Catalysts

ABSTRACT

A complex containing a ligand of formula (I): 
     
       
         
         
             
             
         
       
         
         
           
             useful in the formation of olefin polymerization catalysts and their use in olefin polymerization.

This application is a continuation of U.S. application Ser. No.12/675,545 filed May 12, 2010, pending, which in turn is the U.S.national phase of International Application No. PCT/EP2008/007007 filed27 Aug. 2008 which designated the U.S. and claims priority to EPApplication No. 07016767.1 filed 27 Aug. 2007, the entire contents ofeach of which are hereby incorporated by reference.

This invention relates to complexes of bridged asymmetric η-ligandsuseful in the formation of olefin polymerisation catalysts, as well asthe catalysts themselves and the use therefore in olefin polymerisation.In particular, the invention relates to complexes which compriseasymmetric ligands which are bridged between the 4-7 position of anindenyl group and the 5-membered ring of a cyclopentadienyl containingligand.

The use of metal complexes in the polymerisation of olefins is wellknown. Countless academic and patent publications describe the use ofcatalysts such as metallocenes in olefin polymerisation. Metallocenesare now used industrially and polyethylenes in particular are oftenproduced using cyclopentadienyl based catalyst systems with all mannerof different substitution patterns.

Most metallocene complexes however, are based on symmetrical Π-bondingligands systems such as cyclopentadienyls and indenyls in conjunctionwith a variety of sigma ligands, typically chlorides, and are unbridged.Where bridges are used between ligands, these are typically formed fromthe 1-position of a to the 1-position of another cyclopentadienyl group.The art is replete with disclosures of such compounds. Moreover, bridgedmetallocenes tend to be symmetrical giving rise to meso/rac isomerism.

There remains however, a need to find new catalyst materials for olefinpolymerisation as each new catalyst can impart different properties tothe formed polymer and can exhibit potentially beneficial levels ofactivity. In particular, new catalysts can provide increased Mw and goodcomonomer incorporation and hydrogen response. This has special benefitsfor HDPE and MDPE.

The present inventors have found a new class of olefin polymerisationcatalysts not previously described in the art. The complexes required toform the catalysts of the invention are, inter alia, asymmetric andbridged by a bridge linking the 4-7 position of a indenyl ring to acyclopentadienyl ring.

Bridges from the 4-position of an indenyl ring are not new. WO96/38458describes complexes bridged between the 4-position of two indenylligands.

Asymmetric bridged metallocenes are not new either. WO01/40238 describesa metallocene in which an indenyl group is connected by a methylenebridge via its 4-position to a cyclopentadienyl moiety. WO2006/065906describes bridged indenyl ligand systems in which halogen substituentsare present. WO2006/065809 and WO2005108435 describe indenyl ligandsbridged using group 15 and 16 atoms such as phosphorus and WO2005/105864describes bridged indenyl ligand systems in which aromatic heterocyclesare bound to the indenyl ring system.

The present inventors have found that bridged indenyl complexes wherethe bridge is carbon or silicon based and links the 4-7 position of anindenyl group to the five membered ring of a cyclopentadienyl containingligand are very valuable in that they provide polymers of high Mw andhigh productivity. Normally, high molecular weight polymers are formedin processes where catalyst activity is reduced but the presentcatalysts have been found to produce high Mw polymers without asignificant reduction in productivity.

Thus, viewed from one aspect the invention provides a complex comprisinga ligand of formula (I):

wherein

each R¹, which may be the same or different, is hydrogen, an optionallysubstituted C₁₋₂₀ hydrocarbyl group, N(R⁵)₂, silyl, siloxy; anoptionally substituted heteroaryl group, an optionally substitutedheterocyclyl group or two R¹ groups on adjacent carbon atoms takentogether may form an optionally substituted 5- to 8-membered fused ring;

each R², which may be the same or different is hydrogen, is hydrogen, anoptionally substituted C₁₋₂₀ hydrocarbyl group, N(R⁵)₂, silyl, siloxy;an optionally substituted heteroaryl group, or an optionally substitutedheterocyclyl group;

R³, which binds to the 6-membered ring of the indenyl group, is—(Si(R⁵)₂)_(p)—, where p is 1 or 2, —(C(R₅)₂)n- where n is an integer of2 or more;

each R⁴ which may be the same or different, is hydrogen, an optionallysubstituted C₁₋₂₀ hydrocarbyl group, N(R⁵)₂, silyl, siloxy, anoptionally substituted heteroaryl group, an optionally substitutedheterocyclyl group or two R⁴ groups on adjacent carbon atoms takentogether can form an optionally substituted 5- to 8-membered fusedcarbon ring;

each R⁵, which may be the same or different, is hydrogen, an optionallysubstituted C₁₋₂₀ hydrocarbyl group, or two R⁵ groups taken together canform an optionally substituted 5- to 8-membered ring;

a is 0 to 3;

b is 0 to 3

c is 0 to 4;

complexed to a metal ion, M.

Viewed from another aspect the invention provides a complex comprisingformula (II)

-   -   wherein R¹, R², R⁴, R⁵, a, b and c are as hereinbefore defined        and R⁷ is —C(R⁵)₂—;

complexed to a metal ion, M;

with the proviso that R⁷ binds to the 5 or 6 position of the indenylring.

Viewed from another aspect the invention provides an olefinpolymerisation catalyst comprising:

(i) a complex comprising a metal ion coordinated by at least one ligandof formula (I) or (II); and

(ii) a cocatalyst.

Viewed from another aspect the invention provides use in olefinpolymerisation of a catalyst as hereinbefore defined.

Viewed from another aspect the invention provides a process for thepolymerisation of at least one olefin comprising reacting said at leastone olefin with a catalyst as hereinbefore described.

The compounds required to form the complexes of the invention are alsonew and form a further aspect of the invention. Viewed from anotheraspect therefore the invention provides a compound of formula (III) or(IV)

wherein R¹, R², R³, R⁴, R⁵, R⁷, a, b and c are as hereinbefore defined.

Throughout the description the following definitions are employed.

The term C₁₋₂₀ hydrocarbyl group, as used herein, covers any C₁₋₂₀ groupcomprising carbon and hydrogen only and therefore includes C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ cycloalkenyl,C₆₋₂₀ aryl groups, C₇₋₂₀ alkylaryl groups or C₇₋₂₀ arylalkyl groups.Unless otherwise stated, preferred C₁₋₂₀ hydrocarbyl groups are C₁₋₂₀alkyl groups or C₆₋₂₀ aryl groups, especially C₁₋₈ alkyl groups or C₆₋₁₀aryl groups. Most especially preferred hydrocarbyl groups are methyl,ethyl, propyl, isopropyl, tertbutyl, phenyl or benzyl.

The term halo includes fluoro, chloro, bromo and iodo groups, especiallychloro groups.

The term silyl means a group of formula (R⁵)₃Si— where R⁵ has themeaning as hereinbefore defined. Highly preferred silyl groups are thoseof formula (C₁₋₆ alkyl)₃Si—, especially trimethylsilyl ortertbutyldimethylsiloxy.

The term siloxy means a group of formula (R⁵)₃SiO— where R⁵ has themeaning as hereinbefore defined. Highly preferred siloxy groups arethose of formula (C₁₋₆ alkyl)₃SiO—, especially trimethylsiloxy ortertbutyldimethylsiloxy.

The term heteroaryl means a monocyclic or multicyclic aromatic ringstructure comprising at least one heteroatom. Preferred heteroarylgroups have up to 20 carbon atoms, preferably up to 10 carbon atoms.Preferred heteroaryl groups have 1 to 4 heteroatoms selected from O, Sand N, especially O and N. Preferred heteroaryl groups include pyridyl,pyrrolyl, furyl, indolyl, indolizinyl, benzofuranyl or benzothienylgroups.

The term heterocyclyl means a monocyclic or polycyclic (non aromatic)ring structure comprising at least one heteroatom. Preferredheterocyclic groups have up to 20 carbon atoms, preferably up to 10carbon atoms. Preferred heterocyclic groups have 1 to 3 heteroatomsselected from O, S, and N, especially O and N. Preferred heterocyclicgroups include piperidinyl, furanyl, piperazinyl diazines, oxazolinyl,or thionyl.

The term optionally substituted is used herein to allow for the presenceof one or more additional substituents on a group. Said optionalsubstituents are selected from the group consisting of C₁₋₂₀hydrocarbyl, C₁₋₂₀ alkylhalide, C₁₋₂₀ alkylhydroxy, —N(R⁵)₂, silyl,siloxy, hydroxyl, —OCOC₁₋₂₀ alkyl, —NO₂, —CF₃, —SH, —C(═O)R⁵, —C(═O)OR⁵,—C(═O)NR⁵R⁵, —SR⁵, —NR⁵C(═O)R⁵, —OC(═O)R⁵, —OR⁵, heteroaryl, andheterocyclyl.

Preferred optional substituents are C₁₋₆ alkyl, phenyl, NH₂, NMe₂, andtrimethysilyl.

It will be appreciated that the number of optional substituents presentcan vary depending on the nature of the moiety carrying the optionalsubstituents. Preferably however, 1 to 3 such optional substituents willbe present, especially 1. Any optionally substituted moiety can, ofcourse, remain unsubstituted.

The metal ion M can be any metal ion from the periodic table. Preferablythe metal ion is a transition metal or lanthanide ion, especially atransition metal ion, e.g. one from groups 3 to 6 of the periodic table,Specific metal ions of interest include Sc, Y, Ti, Zr, Hf, V, Nb, Ta,Cr, Mo and W. However, the metal is preferably Sc, Y, Cr, Ti, Zr or Hf,most especially Zr of Hf.

The oxidation state of the metal ion is governed primarily by the natureof the metal ion in question and the stability of the individualoxidation states of each metal ion. Typically, however the metal ionswill be in the 3+ or 4+ oxidation state especially 4+.

It will be appreciated that in the complexes of the invention, the metalion M will also be coordinated by other ligands so as to satisfy thevalency of the metal ion and to fill its available coordination sites.The nature of these further ligands can vary greatly but these willgenerally be 6-ligands.

By a σ-ligand is meant a group bonded to the metal at one or more placesvia a single atom, e.g. a hydrogen, halogen, silicon, carbon, oxygen,sulphur or nitrogen atom. Examples of such ligands include:

amido (e.g. NH₂)

halogenides (e.g. chloride and fluoride),

hydrogen,

triC₁₋₁₂ hydrocarbyl-silyl or -siloxy (e.g. trimethylsilyl),

triC₁₋₆ hydrocarbylphosphimido (e.g. triisopropylphosphimido),

C₁₋₁₂ hydrocarbyl or hydrocarbyloxy (e.g. methyl, ethyl, phenyl, benzyland methoxy),

diC₁₋₆ hydrocarbylamido (e.g. dimethylamido and diethylamido), and

5 to 7 ring membered heterocyclyl (e.g. pyrrolyl, furanyl andpyrrolidinyl).

Highly preferred 6-ligands are chloro, C₁₋₆ alkyl, benzyl and amido(e.g. —NH₂ or NMe₂.

Preferred complexes of the invention therefore comprise

wherein each X is a sigma ligand and all other variables are as hereinbefore defined.

In the ligands of the invention, the subscript “a” is preferably 0, i.e.the 5-membered ring of the indenyl is preferably unsubstituted or “a” is1 or 2, preferably 1. If one substituent is present then it ispreferably in the 2-position of the 5-membered ring.

The substituent is preferably a C₁₋₆-alkyl group, especially methyl ortertbutyl, or is phenyl. Highly preferably, the substituent is 2-methyl.Where more than one substituent is present it is preferred if these arethe same.

In the ligands of the invention, the subscript “b” is preferably 0, i.e.the 6-membered ring of the indenyl is preferably unsubstituted otherthan by the bridge or “b” is 1. If a substituent is present then it ispreferably not adjacent the bridge. Preferably, the substituent will beon the 5-position of the indenyl ring. The substituent is preferably aC₁₋₆-alkyl, especially methyl or tertbutyl, or is phenyl. Highlypreferably, the substituent is 5-tertbutyl. Where more than onesubstituent is present it is preferred if these are the same.

Still more preferred ligands are those carrying 2 and 5 substituents,especially, 2-methyl-5-tertbutyl.

In the ligands of the invention, the subscript “c” may be 0, 1, 2, 3 or4. If a substituent is present then it is preferably a C₁₋₆alkyl group,especially methyl, tert butyl or phenyl. Where more than one substituentis present it is preferred if these are the same.

In a further preferred embodiment therefore, the Cp ring is substitutedby 4 C₁₋₆-alkyl groups, e.g. 4 methyl groups.

In a further highly preferred embodiment two R⁴ groups attached toadjacent ring atoms together form an optionally substituted 6-memberedfused carbon ring which can be saturated or more preferably unsaturatedso as to form an indenyl type structure with the five membered ring. Ina further preferred embodiment, the two remaining R⁴ groups may also betaken together to form an optionally substituted 6-membered fused ringwhich can be saturated or more preferably unsaturated so as to form anfluorenyl type structure.

It is, of course, possible for one R⁴ group to represent a C₁₋₆ alkyl orthe like and two other R⁴ groups may also be taken together to form anoptionally substituted 6-membered fused ring, i.e. c is 3 in thisscenario.

Where further ring structures are present, these may be optionallysubstituted as discussed above, e.g. with C₁₋₆ alkyl groups or phenyl.The bridging group R³ however must bind to the five membered ring in anysuch ligand as depicted in formula (I).

The nature of the R⁵ substituent will vary depending on the nature ofthe atom to which it is attached. Preferred —N(R⁵)₂ groups are NH₂ andNMe₂. Any R⁵ groups present are thus preferrably identical and arepreferably hydrogen or C₁₋₆-alkyl. A further preferred embodiment iswhere two R⁵ groups form a 6-membered ring with the N atom to which theyare attached.

R³ is preferably bound to the 4 or 7 position of the indenyl group. R³is preferably CR⁵ ₂CR⁵ ₂ or SiR⁵ ₂.

Preferably both R⁵ groups on the bridge are the same. More preferablyboth R⁵ groups are C₁₋₆alkyl groups, especially methyl, or hydrogen.Highly preferred groups R³ are SiMe₂ or CH₂CH₂.

R⁷ is CR⁵ ₂ with preferred R⁵ groups as above. A highly preferred groupR⁷ is CH₂.

Highly preferred complexes of the invention are therefore of formula (V)

Wherein R⁴ and c are as hereinbefore defined, R^(1′) is hydrogen orC₁₋₆₋alkyl; R^(2′) is hydrogen or C₁₋₆₋alkyl; and R^(3′) is SiMe₂ orCH₂CH₂.

Certain further complexes also form an aspect of the invention. Thesecatalysts comprise CR⁵ ₂, bridges, especially methylene bridges, fromthe 4 or 7 position of the indenyl ring but have particular substitutionpatterns on the ring.

The catalysts of the invention may exist in diastereomeric forms. Theinvention covers these forms as a mixture of individually.

Throughout the disclosure above, where a narrower definition of asubstituent is presented, that narrower definition is deemed disclosedin conjunction with all broader and narrower definitions of othersubstituents in the application.

Synthesis

The ligands required to form the cataysts of the invention can besynthesised by any process and the skilled organic chemist would be ableto devise various synthetic protocols for the manufacture of thenecessary ligand materials. The prior art is replete with description ofthe formation of bridged metallocenes and the principles by which thesecompounds are made are applicable here to.

The crucial step in the formation of the ligands of the invention is ofcourse, the formation of the bridging group at the 4 to 7 position ofthe indenyl ring. Whilst the skilled man is able to devise variousmethods of achieving this, one such method for each of the preferredbridges of the invention is presented below.

Intermediate

A useful intermediate in the formation of all the necessary bridges is acompound of formula (X)

This compound can be prepared from a toluene analogue which isbrominated both alpha to the methyl group and on the methyl group beforethe formation of the five membered ring as shown below in Scheme 1.

It will be appreciated that different substituents can be introducedonto compounds of formula (X) using known chemistry. For example, analkyl group could be introduced at the 1 position (carbonyl) if it isreacted with a grignard reagent before the resulting hydroxy group iseliminated.

Silyl Bridges

Once formed the compound of formula (X) or analoguous compounds can bereduced to form a 4-bromoindene structure. Formation of a silyl bridgeprecursor is then easily effected by conversion of the bromoindene intoa grignard type structure using magnesium and nucleophilic substitutionwith for example, with SiMe₂Cl₂.

Ethylene Bridges

To form an ethylene bridge an ethyl group needs to be added to indenegroup at an appropriate position. This can be achieved through thereaction of a suitable anion with ethylene oxide as shown in Scheme 4below. The hydroxyl group formed is readily converted into a more activeleaving group, e.g. bromide, to allow easy reaction with the other ηligands presented as nucleophiles or through grignard chemistry asabove. The indene rings are formed simply by reductive elimination ofmethanol using tosyl alcohol. This can be effected before bridgeformation or after bridge formation.

Methylene Bridges

These can also be made from the intermediate above if in a first stepthe carbonyl is converted to an alkoxy group (e.g. by reduction of thecarbonyl and reaction of hydroxide with a suitable electrophile). The Brcan then be replaced by —CHO, reduced to hydroxymethyl and activated,e.g. by tosylation or conversion to a bromide to form an electrophilicspecies capable of reaction with a cyclopentadienyl nucleophile. Theindene ring is formed by elimination of the alkoxy group. Thesereactions are summarised below in Scheme 5.

5/6 Position BridgeBridges at the 5 or 6 position can be introduced using the availablestarting material:

The OH group can be converted to Br using Ph₃PBr₂ and the resultingketobromide manipulated as described above in connection with compound(X) and ethylene or silyl bridges.

Bridge Formation

Once a suitable indene compound has been produced carrying a precursorto a bridge at an appropriate position in the indenyl ring, the actualformation of the bridged complex is trivial as a cyclopentadienyl ionacts as a nucleophile displacing the leaving group from the bridgeprecursor thereby forming a bridged ligand. The cyclopentadienyl ionemployed will, preferably, be functionalised as desired prior toformation of the bridged ligand.

Formation of the desired complex is effected by reacting the desiredligand with an appropriate quantity of base, e.g. an organolithiumcompound, such as methyllithium or butyllithium.

The ligand can then be metallated conventionally, e.g. by reaction witha halide of the metal, preferably in an organic solvent, e.g. ahydrocarbon or a hydrocarbon/ether mixture or ether (THF). The metalhalide can, of course, contain substituents other than halides althoughtypically the ligand is MCl₃ or especially MCl₄.

An alternative approach to the complexes is also envisaged where theligand is reacted with M(NMe₂)₄ or M(CH₂Ph)₄. The resulting complexesmay therefore contain amino or benzyl sigma ligands rather than halideligands. In essence, as long as their are groups to displace, any metalcompound can be used to form the complexes of the invention depending onthe nature of any other ligands which the skilled man wants to bepresent.

σ-ligands other than chlorine may, however, also be introduced bydisplacement of chlorine from a complex metal chloride by reaction withappropriate nucleophilic reagent (e.g. methyl lithium or methylmagnesiumchloride) or using, instead of a metal halide, a reagent such astetrakisdimethylamidotitanium or metal compounds with mixed chloro anddimethylamido ligands.

Catalysts

To form an active catalytic species it is normally necessary to employ acocatalyst as is well known in the art. Cocatalysts used to activatemetallocene catalysts are suitable for use in this invention. Complexand cocatalyst may be introduced into the polymerization reactorseparately or together or, more preferably they are pre-reacted andtheir reaction product is introduced into the polymerization reactor.

As mentioned above, the olefin polymerisation catalyst system of theinvention comprises (i) a complex in which the metal ion is coordinatedby a ligand of the invention; and normally (ii) an aluminium alkylcompound (or other appropriate cocatalyst), or the reaction productthereof.

While the aluminium alkyl compound may be an aluminium trialkyl (e.g.triethylaluminium (TEA)) or an aluminium dialkyl halide (e.g. diethylaluminium chloride (DEAC)), it is preferably an alumoxane, either MAO oran alumoxane other than MAO, such as an isobutylalumoxane, e.g. TIBAO(tetraisobutylalumoxane) or HIBAO (hexaisobutylalumoxane).Alternatively, however, the alkylated (e.g. methylated) catalysts of theinvention may be used with other cocatalysts, e.g. boron compounds suchas B(C₆F₅)₃, C₆H₅N(CH₃)₂H:B(C₆F₅)₄, (C₆H₅)₃C:B(C₆F₅)₄ orNi(CN)₄[B(C₆F₅)₃]₄ ².

However, when the metal in the catalyst is a group 3 transition metal,i.e. Sc, Y, La or Ac, a co-activator may not necessarily be requiredsince such catalyst species are already in an active form.

If desired the complex, complex/cocatalyst mixture or acomplex/cocatalyst reaction product may be used in unsupported form,i.e. complex and MAO can be precipitated without an actual carriermaterial and used as such. However the complex or its reaction productwith the cocatalyst is preferably introduced into the polymerizationreactor in supported form, e.g. impregnated into a porous particulatesupport.

The particulate support material used is preferably an organic orinorganic material, e.g. a polymer (such as for example polyethylene,polypropylene, an ethylene-propylene copolymer, another polyolefin orpolystyrene or a combination thereof). Such polymeric supports may beformed by precipitating a polymer or by a prepolymerization, e.g. ofmonomers used in the polymerization for which the catalyst is intended.However, the support is especially preferably a metal or metalloid oxidesuch as silica, alumina or zirconia or a mixed oxide such assilica-alumina, in particular silica, alumina or silica-alumina.

Particularly preferably, the support material is acidic, e.g. having anacidity greater than or equal to silica, more preferably greater than orequal to silica-alumina and even more preferably greater than or equalto alumina. The acidity of the support material can be studied andcompared using the TPD (temperature programmed desorption of gas)method. Generally the gas used will be ammonia. The more acidic thesupport, the higher will be its capacity to adsorb ammonia gas. Afterbeing saturated with ammonia, the sample of support material is heatedin a controlled fashion and the quantity of ammonia desorbed is measuredas a function of temperature.

Especially preferably the support is a porous material so that thecomplex may be loaded into the pores of the support, e.g. using aprocess analogous to those described in WO94/14856 (Mobil), WO95/12622(Borealis) and WO96/00243 (Exxon). The particle size is not critical butis preferably in the range 5 to 200 μm, more preferably 20 to 80 μm.

Before loading, the particulate support material is preferably calcined,i.e. heat treated, preferably under a non-reactive gas such as nitrogen.This treatment is preferably at a temperature in excess of 100° C., morepreferably 200° C. or higher, e.g. 200-800° C., particularly about 300°C. The calcination treatment is preferably effected for several hours,e.g. 2 to 30 hours, more preferably about 10 hours.

The support may be treated with an alkylating agent before being loadedwith the catalyst. Treatment with the alkylating agent may be effectedusing an alkylating agent in a gas or liquid phase, e.g. in an organicsolvent for the alkylating agent. The alkylating agent may be any agentcapable of introducing alkyl groups, preferably C₁₋₆ alkyl groups andmost especially preferably methyl groups. Such agents are well known inthe field of synthetic organic chemistry. Preferably the alkylatingagent is an organometallic compound, especially an organoaluminiumcompound (such as trimethylaluminium (TMA), dimethyl aluminium chloride,triethylaluminium) or a compound such as methyl lithium, dimethylmagnesium, triethylboron, etc.

The quantity of alkylating agent used will depend upon the number ofactive sites on the surface of the carrier. Thus for example, for asilica support, surface hydroxyls are capable of reacting with thealkylating agent. In general, an excess of alkylating agent ispreferably used with any unreacted alkylating agent subsequently beingwashed away.

Following treatment of the support material with the alkylating agent,the support is preferably removed from the treatment fluid and anyexcess treatment fluid is allowed to drain off.

The optionally alkylated support material is loaded with the catalyst.This loading may be effected by using a solution of the catalyst in anorganic solvent therefor, e.g. as described in the patent publicationsreferred to above. Preferably, the volume of catalyst solution used isfrom 50 to 500% of the pore volume of the carrier, more especiallypreferably 80 to 120%. The concentration of catalyst compound in thesolution used can vary from dilute to saturated depending on the amountof metallocene active sites that it is desired be loaded into thecarrier pores.

The active metal (i.e. the metal of the catalyst) is preferably loadedonto the support material at from 0.1 to 4%, preferably 0.5 to 3.0%,especially 1.0 to 2.0%, by weight metal relative to the dry weight ofthe support material.

After loading of the catalyst onto the support material, the loadedsupport may be recovered for use in olefin polymerization, e.g. byseparation of any excess catalyst solution and if desired drying of theloaded support, optionally at elevated temperatures, e.g. 25 to 80° C.

Alternatively, a cocatalyst, e.g. an alumoxane or an ionic catalystactivator (such as a boron or aluminium compound, especially afluoroborate) may also be mixed with or loaded onto the catalyst supportmaterial. This may be done subsequently or more preferablysimultaneously to loading of the complex, for example by including thecocatalyst in the solution of the catalyst, by contacting the catalystloaded support material with a solution of the cocatalyst or catalystactivator, e.g. a solution in an organic solvent, or by firstimpregnating the cocatalyst with a support and then contacting thecocatalyst impregnated support with a solution of the catalyst or neatcatalyst (e.g. as described in WO96/32423). Alternatively however anysuch further material may be added to the catalyst-loaded supportmaterial in the polymerization reactor or shortly before dosing of thecatalyst material into the reactor.

In this regard, as an alternative to an alumoxane it may be preferred touse a fluoroborate catalyst activator for the alkylated catalysts,especially a B(C₆F₅)₃ or more especially a —B(C₆F₅)₄ compound, such asC₆H₅N(CH₃)₂H:B(C₆F₅)₄ or (C₆H₅)₃C:B(C₆F₅)₄. Other borates of generalformula (cation)_(a) (borate)_(b) where a and b are positive numbers,may also be used.

As an alternative to the loading of the optionally alkylated supportmaterial with a solution of the procatalyst in an organic solvent,loading of the catalyst may be effected by mixing it with the optionallyalkylated support material in the absence of solvents with said carrierat a temperature of at least 50° C. but less than the vaporisationtemperature of the metallocene compound. The particular features of thisso-called dry mixing method are disclosed in WO 96/32423 (Borealis). Ifuse of a cocatalyst/catalyst activator in such process is desired, thismay be impregnated into the optionally alkylated support material priorto loading of the catalyst.

Where such a cocatalyst or catalyst activator is used, it is preferablyused in a mole ratio to the metallocene of from 0.1:1 to 10000:1,especially 1:1 to 50:1, particularly 1:2 to 30:1. More particularly,where an alumoxane cocatalyst is used, then for an unsupported catalystthe aluminium:metallocene metal (M) molar ratio is conveniently 2:1 to10000:1, preferably 50:1 to 1000:1. Where the catalyst is supported theAl:M molar ratio is conveniently 2:1 to 10000:1 preferably 50:1 to400:1. Where a borane cocatalyst (catalyst activator) is used, the B:Mmolar ratio is conveniently 2:1 to 1:2, preferably 9:10 to 10:9,especially 1:1. When a neutral triarylboron type cocatalyst is used theB:M molar ratio is typically 1:2 to 500:1, however some aluminium alkylwould normally also be used. When using ionic tetraaryl boratecompounds, it is preferred to use carbonium rather than ammoniumcounterions or to use B:M molar ratio 1:1.

Where the further material is loaded onto the catalyst loaded supportmaterial, the support may be recovered and if desired dried before usein olefin polymerization.

The olefin polymerized using the catalyst of the invention is preferablyethylene or an alpha-olefin or a mixture of ethylene and an α-olefin ora mixture of alpha olefins, for example C₂₋₂₀ olefins, e.g. ethylene,propene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene etc. Theolefins polymerized in the method of the invention may include anycompound which includes unsaturated polymerizable groups. Thus forexample unsaturated compounds, such as C₆₋₂₀ olefins (including cyclicand polycyclic olefins (e.g. norbornene)), and polyenes, especiallyC₄₋₂₀ dienes, may be included in a comonomer mixture with lower olefins,e.g. C₂₋₅ α-olefins. Diolefins (i.e. dienes) are suitably used forintroducing long chain branching into the resultant polymer. Examples ofsuch dienes include am linear dienes such as 1,5-hexadiene,1,6-heptadiene, 1,8-nonadiene, 1,9-decadiene, etc.

In general, where the polymer being produced is a homopolymer it willpreferably be polyethylene or polypropylene. Where the polymer beingproduced is a copolymer it will likewise preferably be an ethylene orpropylene copolymer with ethylene or propylene making up the majorproportion (by number and more preferably by weight) of the monomerresidues. Comonomers, such as C₄₋₆ alkenes, will generally beincorporated to contribute to the mechanical strength of the polymerproduct.

Polymerization in the method of the invention may be effected in one ormore, e.g. 1, 2 or 3, polymerization reactors, using conventionalpolymerization techniques, e.g. gas phase, solution phase, slurry orbulk polymerization.

In general, a combination of slurry (or bulk) and at least one gas phasereactor is often preferred, particularly with the reactor order beingslurry (or bulk) then one or more gas phase.

For slurry reactors, the reaction temperature will generally be in therange 60 to 110° C. (e.g. 85-110° C.), the reactor pressure willgenerally be in the range 5 to 80 bar (e.g. 50-65 bar), and theresidence time will generally be in the range 0.3 to 5 hours (e.g. 0.5to 2 hours). The diluent used will generally be an aliphatic hydrocarbonhaving a boiling point in the range −70 to +100° C. In such reactors,polymerization may if desired be effected under supercriticalconditions.

For gas phase reactors, the reaction temperature used will generally bein the range 60 to 115° C. (e.g. 70 to 110° C.), the reactor pressurewill generally be in the range 10 to 25 bar, and the residence time willgenerally be 1 to 8 hours. The gas used will commonly be a non-reactivegas such as nitrogen together with monomer (e.g. ethylene).

For solution phase reactors, the reaction temperature used willgenerally be in the range 130 to 270° C., the reactor pressure willgenerally be in the range 20 to 400 bar and the residence time willgenerally be in the range 0.005 to 1 hour. The solvent used willcommonly be a hydrocarbon with a boiling point in the range 80-200° C.

Generally the quantity of catalyst used will depend upon the nature ofthe catalyst, the reactor types and conditions and the propertiesdesired for the polymer product. Conventional catalyst quantities, suchas described in the publications referred to herein, may be used.

The polymer produced using the catalysts of the invention will generallypossess a high Mw, e.g. greater than 200,000, preferably greater than400,000, more preferably greater than 600,00, especially more than800,000. Such polymers are ideally used for MDPE and HDPE applications,i.e. where the density of the polymer is 930 kg/m3 or greater,especially 940 kg/m3 or greater.

The polymers made by the catalysts of the invention are useful in allkinds of end articles such as pipes, films, moulded articles (e.g.injection moulded, blow moulded, rotomoulded articles), extusioncoatings and so on.

The invention will now be illustrated by reference to the followingnon-limiting Examples:

EXPERIMENTAL

The following instrumentation was used:

NMR spectroscopy: Bruker DPX 300 NMR spectrometer

IR spectroscopy: Nicolet 5700 FT-IR spectrometer equipped with a SmartOrbit diamond ATR unit

Single crystal structure analysis: Nonius Kappa-CCD equipped withgraphite-monochromated Mo—K(alpha) radiation

Ligand and Complex Synthesis

Example 1 4-(Bromomethyl)-1-methoxy-2-methylindane

To a solution of 48.2 g (0.2 mol) of 4-bromo-2-methyl-methoxyindane in700 ml of THF 80.0 ml 2.5 M (0.2 mol) n-BuLi in hexanes was added for 10min at −80° C. The resulting mixture was stirred for 2 h at thistemperature, then cooled to −110° C., and 18.7 ml (17.6 g, 0.241 mol) ofDMF was added at vigorous stirring. This mixture was warmed to roomtemperature, 10 ml of water was added, and then the resulting mixturewas evaporated in vacuum. To a solution of the residue in 1050 ml of amixture of THF-methanol (2:1, vol.), 15.1 g (0.4 mol) of NaBH₄ was addedin small portions at vigorous stirring for ca. 5 min. This mixture wasstirred for 15 min at room temperature and then evaporated to dryness.To the residue 500 ml of warm water was added, and the crude alcohol wasextracted with 3×200 ml of methylene dichloride. The combined organicextract was dried over Na₂SO₄ and then evaporated to dryness. To amixture of the residue, 52.5 g (0.2 mol) of PPh₃, and 800 ml of THF 35.6g (0.2 mol) of NBS was added for ca. 5 min at 20° C. The resultingmixture was stirred for 5 min and evaporated to dryness. A mixture ofthe residue with 500 ml of hexanes was filtered through glass frit (G3).The precipitate was additionally washed by 3×300 ml of hexanes. Thecombined organic extract was evaporated to dryness. The product wasisolated using short column with Silica Gel 60 (40-63 um, d 130 mm, l100 mm, eluent hexanes/ether=20/1, vol.). Yield 37.8 Γ (74%) of a ca. 1to 1.5 mixture of two diastereomers.

Anal. calc. for C₁₂H₁₅BrO: C, 56.49; H, 5.93. Found: C, 56.60; H, 6.04.

¹H NMR (C₆D₆): δ 7.11-7.32 (m, 6H, 5,6,7-H in indenyl of both isomers),4.47 (d, J=5.6 Hz, 1H, MeOCH of minor isomer), 4.41 (s, 2H, CH₂Br ofmajor isomer), 4.40 (s, 2H, CH₂Br of minor isomer), 4.37 (d, J=4.1 Hz,1H, MeOCH of major isomer), 3.42 (s, 3H, OMe of major isomer), 3.36 (s,3H, OMe of minor isomer), 3.22 (dd, J=15.7 Hz, J=7.3 Hz, 1H, 3-CHH′ ofmajor isomer), 2.95 (dd, J=15.7 Hz, J=7.1 Hz, 1H, 3-CHH′ of minorisomer), 2.41-2.71 (m, 4H, 3-CHH′ and CHMe of both isomers), 1.16 (d,J=7.0 Hz, 3H, 2-Me of major isomer), 1.10 (d, J=6.9 Hz, 3H, 2-Me ofminor isomer).

¹³C{¹H} NMR (C₆D₆), major isomer: δ 137.9, 137.43, 137.40, 123.4, 121.3,120.0, 85.4, 50.8, 33.9, 30.7, 25.7, 13.7.

7-(Bromomethyl)-2-methyl-1H-indene

To a solution of 37.5 g (0.147 mol) of4-(bromomethyl)-1-methoxy-2-methylindane in 600 ml of toluene 3.12 g(16.4 mmol) of TsOH was added at 110° C. This mixture was refluxed withDean-Stark trap within 12 min and then passed through short column withSilica Gel 60 (40-63 um, d 90 mm, l 80 mm). The Silica Gel layer wasadditionally washed by 500 ml of toluene. The combined elute wasevaporated to dryness. The product was isolated by flash chromatographyon short column with Silica Gel 60 (40-63 um, d 90 mm, l 80 mm; eluent:hexanes). Yield 33.2 g (97%).

Anal. calc. for C₁₁H₁₁Br: C, 59.22; H, 4.97. Found: C, 59.47; H, 5.11.

¹H NMR (CDCl₃): δ 7.19-7.23 (m, 2H, 4,6-H), 7.10 (m, 1H, 5-H), 6.50 (m,1H, 3-H), 4.56 (s, 2H, CH₂Br), 3.36 (br.s, 2H, 1,1′-H), 2.19 (m, 3H,2-Me).

¹³C{¹H} NMR (CDCl₃): δ 146.6, 146.2, 142.4, 132.0, 127.17, 127.14,124.4, 120.2, 40.9, 31.7, 16.7.

Chloro(dimethyl)(2-methyl-1H-inden-7-yl)silane

To 1.63 g (67 mmol) of magnesium turnings (activated by 0.2 ml of1,2-dibromoethane for 10 min) in 50 ml of THF a solution of 11.6 g (55mmol) of 2-methyl-7-bromoindene in 350 ml of THF was added dropwise atvigorous stirring for ca. 40 min. This mixture was additionally refluxedfor 1 h, and then cooled to room temperature. The Grignard reagentobtained was added dropwise at vigorous stirring to a solution of 21.4 g(166 mmol) of dichlorodimethylsilane in 50 ml of THF for 1 h at roomtemperature. The resulting mixture was stirred for 12 h and thenevaporated to dryness. The residue was dissolved in 100 ml of ether, andthe solution obtained was filtered through glass frit (G3). Theprecipitate was additionally washed by 3×50 ml of ether. The combinedether solution was evaporated to dryness, and the residue was distilledin vacuum, by 110-112° C./1 mm Hg. Yield 9.80 Γ (80%).

Anal. calc. for C₁₂H₁₅ClSi: C, 64.69; H, 6.79. Found: C, 64.88; H, 6.55.

¹H NMR (CDCl₃): δ 7.42-7.47 (m, 2H, 4,6-H), 7.34-7.39 (m, 1H, 5-H), 6.60(m, 1H, 3-H), 3.55 (br.s, 2H, 1,1′-H), 2.28 (br.s, 3H, 2-Me), 0.86 (s,6H, Me₂SiCl).

¹³C{¹H} NMR (CDCl₃): δ 148.5, 146.3, 145.6, 129.8, 128.5, 126.8, 125.9,122.0, 43.6, 16.7, 2.5.

Example 2 2-(1-Methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethanol

To a solution of 20.0 g (82.9 mmol) of 4-bromo-2-methyl-methoxyindane in200 ml of THF 33.2 ml of 2.5 M (83.0 mmol) n-BuLi in hexanes was addedfor 20 min at −80° C. This mixture was stirred for 40 min at thistemperature, cooled to −110° C., and 4.38 g (99.4 mmol) of ethyleneoxide was added by one portion at vigorous stirring. The resultingmixture was stirred for 12 h at room temperature, and then 10 ml ofwater was added. The organic layer was separated and evaporated todryness. To the residue 200 ml of water was added, and the crude productwas extracted with 3×100 ml of dichloromethane. The combined organicextract was dried over Na₂SO₄ and evaporated to dryness. The product wasisolated by flash chromatography using short column with Silica Gel 60(40-63 um, d 110 mm, 190 mm; eluent: hexanes/ether=20/1). Yield 12.7 g(74%) of a ca. 1 to 1.2 mixture of two diastereomers.

Anal. calc. for C₁₃H₁₈O₂: C, 75.69; H, 8.80. Found: C, 75.87; H, 8.93.

¹H NMR (CDCl₃): δ 7.29 (m, 2H, 6-H of both isomers), 7.23 (m, 2H, 7-H ofboth isomers), 7.15 (m, 2H, 5-H of both isomers), 4.58 (d, J=5.5 Hz, 1H,CHOMe of minor isomer), 4.48 (d, J=4.0 Hz, 1H, CHOMe of major isomer),3.53 (s, 3H, OMe of major isomer), 3.48 (s, 3H, OMe of minor isomer),3.74 (m, 4H, CH₂Br of both isomers), 3.27 (dd, J=15.9 Hz, J=7.7 Hz, 1H,3-CHH′ of major isomer), 2.97 (dd, J=15.0 Hz, J=6.8 Hz, 1H, 3-CHH′ ofminor isomer), 2.82 (m, 4H, CH₂CH₂Br of both isomers), 2.73 (dd, J=15.0Hz, J=7.0 Hz, 1H, 3-CHH′ of minor isomer), 2.54-2.71 (m, 4H, CHMe and OHof both isomers), 2.46 (dd, J=15.9 Hz, J=5.0 Hz, 1H, 3-CHH′ of majorisomer), 1.18 (d, J=7.0 Hz, 3H, 2-Me of major isomer), 1.15 (d, J=7.9Hz, 3H, 2-Me of minor isomer).

¹³C{¹H} NMR (CDCl₃): δ 142.6, 142.4, 141.9 (2C), 134.8, 134.6, 128.9,128.7, 126.6, 126.2, 123.4, 123.2, 91.4, 86.1, 62.3, 62.2, 56.6, 56.2,39.1, 38.3, 36.8, 36.5, 36.4, 36.2, 19.3, 13.5.

4-(2-Bromoethyl)-1-methoxy-2-methylindane

To a mixture of 41.3 g (0.2 mol) of2-(1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethanol and 52.5 g (0.2mol) PPh₃ in 800 ml of THF 35.6 g (0.2 mol) of NBS was added at vigorousstirring for 5 min at 0° C. This mixture was stirred for 2 h at roomtemperature and then evaporated to dryness. A solution of the residue in500 ml of hexanes was filtered through glass frit (G3), and theprecipitate was additionally washed by 3×300 ml hexanes. The combinedorganic extract was evaporated to dryness. The product was isolated fromthe residue using flash chromatography on Silica Gel 60 (40-63 um, d 80mm, l 250 mm; eluent: hexanes/ether=20/1, vol.). Yield 39.3 g (73%) ofca. 1 to 1 mixture of the diastereomers A and B.

Anal. calc. for C₁₃H₁₇BrO: C, 58.01; H, 6.37. Found: C, 58.26; H, 6.17.

¹H NMR (CDCl₃): δ 7.30 (m, 2H, 6-H in indenyl of A and B), 7.20 (m, 2H,7-H in indenyl of A and B), 7.12 (m, 2H, 5-H in indenyl of A and B),4.52 (m, 1H, 1-H in indenyl of A), 4.41 (m, 1H, 1-H in indenyl of B),3.53 (m, 4H, CH₂CH₂Br of A and B), 3.47 (s, 3H, OMe of B), 3.42 (s, 3H,OMe of A), 3.22 (dd, J=15.8 Hz, J=7.6 Hz, 1H, 3-H in indenyl of B), 3.15(m, 4H, CH₂CH₂Br of A and B), 2.92 (dd, J=14.9 Hz, J=6.7 Hz, 1H, 3-H inindenyl of A), 2.48-2.71 (m, 3H, 2,3-H in indenyl of A and 2-H inindenyl of B), 2.42 (dd, J=15.8 Hz, J=4.8 Hz, 1H, 3-H in indenyl of B),1.18 (d, J=7.1 Hz, 3H, 2-Me in indenyl of B), 1.13 (d, J=6.6 Hz, 3H,2-Me in indenyl of A).

¹³C{¹H} NMR (CDCl₃): δ 143.1, 142.6, 142.2, 141.7, 135.1, 135.0, 128.5,128.4, 126.8, 126.5, 124.1, 123.8, 91.3, 85.9, 56.7, 56.5, 39.4, 38.5,36.80, 36.78, 36.7, 36.5, 31.7, 31.6, 19.4, 13.6.

4/7-(2-Bromoethyl)-2-methyl-1H-indene

To a hot (110° C.) solution of 10.0 g (37.2 mmol) of4-(2-bromoethyl)-1-methoxy-2-methylindane in 200 ml of toluene 0.8 g ofTsOH was added. This mixture was refluxed with Dean-Stark trap for 10min and then passed through the layer of Silica Gel 60 (40-63 um, d 80mm, l 50 mm). The Silica Gel layer was additionally washed by 500 ml oftoluene. The combined organic extract was evaporated to dryness. Theproduct was isolated by flash chromatography using a short column withSilica Gel 60 (40-63 um, d 80 mm, l 50 mm; eluent: hexanes). Yield 8.46g (96%) of a ca. 1 to 1.5 mixture of 4- and7-(2-bromoethyl)-2-methyl-1H-indenes.

Anal. calc. for C₁₂H₁₃Br: C, 60.78; H, 5.53. Found: C, 61.00; H, 5.65.

¹H NMR (CDCl₃): δ 6.92-7.31 (m, 6H, 5,6,7-H and 4,5,6-H of minor andmajor isomers, respectively), 6.60 (m, 1H, 3-H in indenyl of minorisomer), 6.51 (m, 1H, 3-H in indenyl of major isomer), 3.62 (m, 2H,CH₂Br of major isomer), 3.57 (m, 2H, CH₂Br of minor isomer), 3.32 (br.s,2H, 1,1′-H in indenyl of minor isomer), 3.28 (br.s, 2H, 1,1′-H inindenyl of major isomer), 3.27 (m, 2H, CH₂CH₂Br of minor isomer), 3.23(m, 2H, CH₂CH₂Br of major isomer), 2.19 (m, 3H, 2-Me in indenyl of minorisomer), 2.18 (m, 3H, 2-Me in indenyl of major isomer).

Ligand 1

To a solution of 484 mg (6.72 mmol) of CpLi in 80 ml of THF a solutionof 1.50 g (6.72 mmol) of 7-(bromomethyl)-2-methyl-1H-indene in 10 ml ofTHF was added dropwise for 5 min at −80° C. The reaction mixture wasstirred for 1 h at room temperature, 1 ml of water was added, and thenevaporated to dryness. To the residue 100 ml of water was added, and thecrude product was extracted with 3×50 ml of dichloromethane. Thecombined extract was dried over Na₂SO₄ and evaporated to dryness. Theproduct was isolated by flash chromatography using a short column withSilica Gel 60 (40-63 um, d 50 mm, l 50 mm; eluent: hexanes). Yield 1.13g (81%).

Anal. calc. for C₁₆H₁₆: C, 92.26; H, 7.74. Found: C, 92.09; H, 7.58.

¹H NMR (CDCl₃): δ 6.94-7.30 (m, 3H), 6.98-6.66 (m, 4H), 3.76-3.89 (m,2H), 3.23-3.34 (m, 2H), 2.87-3.03 (m, 2H), 2.18 (m, 3H).

Ligand 3

To a solution of 1.30 g (10 mmol) of 2-methyl-1H-indene in 90 ml ofether 4.0 ml of 2.5 M (10 mmol) n-BuLi in hexanes was added at 0° C.This mixture was stirred for 2 h at room temperature, and then asolution of 2.23 g (10 mmol) of 7-(bromomethyl)-2-methyl-1H-indene in 15ml of THF was added dropwise at vigorous stirring for 10 min at −80° C.The resulting mixture was stirred for 12 h at room temperature, and then1 ml of water was added. This mixture was evaporated to dryness, and 100ml of water was added. The crude product was extracted with 3×50 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyusing a short column with Silica Gel 60 (40-63 um, d 60 mm, l 70 mm;eluent: hexanes. Yield 2.50 g (92%) of2-methyl-1-[(2-methyl-1H-inden-7-yl)methyl]-1H-indene.

Anal. calc. for C₂₁1H₂₀: C, 92.60; H, 7.40. Found: C, 92.77; H, 7.53.

¹H NMR (CDCl₃): δ 7.19-7.30 (m, 4H), 7.10 (m, 1H), 6.95 (m, 1H), 6.73(m, 1H), 6.57 (m, 1H), 6.53 (m, 1H), 3.67 (dd, J=10.0 Hz, J=5.6 Hz, 1H,1-H in 2-methylinden-1-yl), 3.30 (dd, J=13.8 Hz, J=5.6 Hz, 1H, CHH′CH),3.17 (m, 2H, 1,1′-H in 2-methylinden-4-yl), 2.61 (dd, J=13.8 Hz, J=10.0Hz, 1H, CHH′CH), 2.17 (br.s, 3H, Me in 2-methylinden-4-yl), 2.13 (br.s,3H, Me in 2-methylinden-1-yl).

¹³C{¹H} NMR (CDCl₃): δ 149.6, 147.1, 145.9, 145.6, 144.4, 142.3, 135.0,127.5, 126.6 (2C), 126.4, 124.5, 123.5, 123.4, 119.7, 118.0, 52.2, 41.6,34.6, 16.7, 15.5.

Ligand 4

To a solution of 1.30 g (10.0 mmol) of 3-methyl-1H-indene in 90 ml ofether 4.0 ml of 2.5 M (10.0 mmol) n-BuLi in hexanes at 0° C. Thismixture was stirred for 2 h at room temperature, then cooled to −80° C.,a solution of 2.23 g (10.0 mmol) of 7-(bromomethyl)-2-methyl-1H-indenein 15 ml of THF was added. The resulting mixture was stirred for 12 h atroom temperature, and then 1 ml of water was added. This mixture wasevaporated to dryness, and 100 ml of water was added. The crude productwas extracted by 3×50 ml of dichloromethane. The combined extract wasdried over Na₂SO₄ and then evaporated to dryness. The product wasisolated from the residue by flash chromatography using short columnwith Silica Gel 60 (40-63 um, d 60 mm, l 50 mm; eluent: hexanes). Yield2.61 g (96%) of 3-methyl-1-[(2-methyl-1H-inden-7-yl)methyl]-1H-indene.

Anal. calc. for C₂₄H₂₀: C, 92.60; H, 7.40. Found: C, 92.69; H, 7.24.

¹H NMR (CDCl₃): δ 7.09-7.35 (m, 7H, 4,5,6-H in 2-methylinden-4-yl and4,5,6,7-H in 3-methylinden-1-yl), 6.55 (m, 1H, 3-H in2-methylinden-4-yl), 6.11 (m, 1H, 2-H in 3-methylinden-1-yl), 3.91 (m,1-H in 3-methylinden-1-yl), 3.24 (m, 2H, 1,1′-H in 2-methylinden-4-yl),3.15 (dd, J=13.4 Hz, J=6.8 Hz, 1H, CHH′CH), 2.66 (dd, J=13.5 Hz, J=9.9Hz, 1H, CHH′CH), 2.18 (br.s, 3H, Me in 2-methylinden-4-yl), 2.16 (m, 3H,Me in 3-methylinden-1-yl).

Ligand 5

To a solution of 1.72 g (10.0 mmol) of 3-tert-butyl-1H-indene in 90 mlof ether 4.0 ml of 2.5 M (10.0 mmol) n-BuLi in hexanes was added at 0°C. This mixture was stirred for 2 h at room temperature, then cooled to−80° C., and a solution of 2.23 g (10.0 mmol) of7-(bromomethyl)-2-methyl-1H-indene in 15 ml of THF was added for 10 min.The resulting mixture was stirred for 12 h at room temperature, and then1 ml of water was added. This mixture was evaporated to dryness, and 100ml of water was added. The crude product was extracted with 3×50 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andthen evaporated to dryness. The product was isolated from the residue byflash chromatography using short column with Silica Gel 60 (40-63 um, d60 mm, 150 mm; eluent: hexanes). Yield 2.89 g (92%) of3-tert-butyl-1-[(2-methyl-1H-inden-7-yl)methyl]-1H-indene.

Anal. calc. for C₂₄H₂₆: C, 91.67; H, 8.33. Found: C, 91.75; H, 5.22.

¹H NMR (CDCl₃): δ 7.67 (m, 1H), 7.20-7.39 (m, 5H), 7.14 (m, 1H), 6.59(m, 1H, 3-H in 2-methylinden-4-yl), 6.13 (m, 1H, 2-H in3-tert-butylinden-1-yl), 3.75 (m, 1-H in 3-tert-butylinden-1-yl), 3.31(s, 1H, 1-H in 2-methylinden-4-yl), 3.29 (s, 1H, 1′-H in2-methylinden-4-yl), 3.22 (dd, J=13.4 Hz, J=6.3 Hz, 1H, CHH′CH), 2.68(dd, J=13.5 Hz, J=9.9 Hz, 1H, CHH′CH), 2.22 (br.s, 3H, Me in2-methylinden-4-yl), 1.41 (s, 9H, tert-Bu).

¹³C{¹H} NMR (CDCl₃): δ 152.0, 149.3, 145.9, 145.6, 143.4, 142.0, 135.4,131.4, 127.5, 126.7, 126.0, 124.3, 124.1, 123.3, 122.2, 117.9, 48.4,41.6, 35.8, 33.0, 29.4, 16.8.

Example 3 4-(9H-Fluoren-9-ylmethyl)-2-methyl-2,3-dihydro-1H-inden-1-ylmethyl ether

To a solution of 3.32 g (0.20 mol) of 9H-fluorene in 500 ml of ether 80ml of 2.5 M (0.20 mol) n-BuLi in hexanes was added at 0° C. This mixturewas stirred for 12 h, cooled to −80° C., and then a solution of 5.10 g(0.20 mol) of 4-(bromomethyl)-1-methoxy-2-methylindane in 150 ml ofether was added dropwise by vigorous stirring for 30 min at thistemperature. The resulting mixture was stirred for 24 h at roomtemperature, and then 500 ml of water was added. The organic layer wasseparated, and the aqueous layer was extracted with 3×200 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyon Silica Gel 60 (40-63 um, d 60 mm, l 150 mm; eluent:hexanes/ether=20/1). Yield 5.31 g (78%) of a mixture of thediastereomers A and B.

Anal. calc. for C₂₅H₂₄O: C, 88.20; H, 7.11. Found: C, 88.39; H, 7.00.

¹HNMR (CDCl₃): δ 7.83 (m, 4H, 4,5-H in fluorenyl of A and B), 7.09-7.46(m, 18H, 1,2,3,6,7,8-H in fluorenyl and 5,6,7-H in indenyl of A and B),4.66 (m, A), 4.53 (m, B), 4.27 (m, 2H, 9-H in fluorenyl of A and B),3.57 (s, 3H, OMe of B), 3.53 (s, 3H, OMe of A), 2.30-3.17 (m, 12H, CH₂bridge and 1,2,3,3′-H in indenyl of A and B), 1.19 (d, J=7.1 Hz, 3H,2-Me in indenyl of B), 1.15 (d, J=6.8 Hz, 3H, 2-Me in indenyl of A).

¹³C{¹H} NMR (CDCl₃): δ 147.0, 146.90, 146.88, 146.85, 142.8, 142.5,142.4, 142.3, 140.62, 140.59, 140.57, 140.54, 136.5, 136.4, 129.4,129.2, 127.05, 127.03, 126.7, 126.6, 126.5, 126.3, 124.73, 124.67,123.5, 123.3, 119.72, 119.71, 99.8, 91.5, 86.1, 56.7, 56.4, 47.64,47.62, 39.4, 38.2, 37.52, 37.46, 37.0, 36.7, 19.4, 13.6.

Ligand 6

To a hot (110° C.) solution of 13.8 g (40.5 mmol) of4-(9H-fluoren-9-ylmethyl)-2-methyl-2,3-dihydro-1H-inden-1-yl methylether in 400 ml of toluene 1.40 g (7.36 mmol) of TsOH was added. Thismixture was refluxed with a Dean-Stark trap for 40 min, and then passedthrough short column with Silica Gel 60 (40-63 um, d 80 mm, l 60 mm).The column was additionally washed with 500 ml of toluene. The combinedelute was evaporated to dryness. The product was isolated by flashchromatography using a short column with Silica Gel 60 (40-63 um, d 60mm, l 70 mm; eluent: hexanes/ether=35/1). Yield 12.0 g (96%) of pure9-[(2-methyl-1H-inden-7-yl)methyl]-9H-fluorene.

Anal. calc. for C₂₄H₂O: C, 93.46; H, 6.54. Found: C, 93.57; H, 6.65.

¹H NMR (CDCl₃): δ 7.82 (m, 2H, 4,5-H in fluorenyl), 7.15-7.43 (m, 9H,1,2,3,6,7,8-H in fluorenyl and 4,5,6-H in indenyl), 6.58 (m, 1H, 3-H inindenyl), 4.35 (t, J=8.0 Hz, 1H, 9-H in fluorenyl), 3.11-3.16 (m, 4H,1,1′-H in indenyl and CH₂), 2.15 (s, 3H, Me).

Ligand 7

To a solution of 971 mg (13.5 mmol) of CpLi in 100 ml of THF a solutionof 3.0 g (13.5 mmol) of chloro(dimethyl)(2-methyl-1H-inden-7-yl)silanein 10 ml of THF was added dropwise by vigorous stirring for 5 min at−80° C. This mixture was additionally stirred for 1 h at roomtemperature, and 1 ml of water was added. The mixture was evaporated todryness, and 100 ml of water was added to the residue. The crude productwas extracted with 3×50 ml of dichloromethane. The combined organicextract was dried over Na₂SO₄ and evaporated to dryness. The product wasisolated from the residue by flash chromatography using a short columnwith Silica Gel 60 (40-63 um, d 60 mm, l 50 mm; eluent: hexanes). Yield2.89 g (85%) of purecyclopenta-2,4-dien-1-yl(dimethyl)(2-methyl-1H-inden-7-yl)silane.

Anal. calc. for C₁₇H₂₀Si: C, 80.89; H, 7.99. Found: C, 81.12; H, 8.10.

¹H NMR (CDCl₃, 20° C.): δ 7.20-7.32 (m, 3H, 4,5,6-H in indenyl), 6.63(br.s, 2H, 3,4-H in Cp), 6.52 (m, 1H, 3-H in indenyl), 6.47 (br.s, 2H,2,5-H in Cp), 3.75 (br.s, 1H, 1-H in Cp), 3.38 (s, 2H, 1,1′-H inindenyl), 2.18 (s, 3H, 2-Me in indenyl), 0.22 (s, 6H, SiMe₂).

¹³C{¹H} NMR (CDCl₃, 20° C.): δ 148.6, 145.8, 145.3, 143.3 (br.), 133.5(br.), 130.6 (br.), 129.2, 127.1, 125.9, 121.0, 44.2, 16.8, −1.7, −3.7.

Ligand 8

To a solution of 1.22 g (10.0 mmol) of tert-butylcyclopentadiene in 100ml of THF 4.0 ml of 2.5 M (10.0 mmol) n-BuLi in hexanes was added at−30° C. This mixture was stirred for 1 h at room temperature, and then asolution of 2.23 g (10.0 mmol) ofchloro(dimethyl)(2-methyl-1H-inden-7-yl)silane in 15 ml of THF was addeddropwise by vigorous stirring for 5 min at room temperature. Thismixture was additionally stirred for 1 h, and 1 ml of water was added.The mixture was evaporated to dryness, and 100 ml of water was added tothe residue. The crude product was extracted with 3×50 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 2.56 g (83%) of pure(3-tert-butylcyclopenta-2,4-dien-1-yl)(dimethyl)(2-methyl-1H-inden-7-yl)silane.

Anal. calc. for C₂₁H₂₈Si: C, 81.75; H, 9.15. Found: C, 81.67; H, 9.30.

¹H NMR (CDCl₃, 20° C.): δ 7.24-7.34 (m, 3H, 4,5,6-H in indenyl), 6.68(br.m, 1H, 4-H in Cp), 6.55 (m, 1H, 3-H in indenyl), 6.46 (br.m, 1H, 5-Hin Cp), 6.07 (br.s, 1H, 2-H in Cp), 3.65 (br.s, 1H, 1-H in Cp), 3.41(br.s, 2H, 1,1′-H in indenyl), 2.21 (s, 3H, 2-Me in indenyl), 1.20 (s,9H, tert-Bu), 0.26 (s, 6H, SiMe₂).

Ligand 9

To a solution of 1.29 g (10.0 mmol, 90% purity) of 1H-indene in 90 ml ofether 4.0 ml of 2.5M (10.0 mmol) n-BuLi in hexanes was added at 0° C.This mixture was stirred for 12 h at room temperature, cooled to −30°C., and 449 mg (5.0 mmol) of CuCN was added. The resulting mixture wasstirred for 1 h at this temperature, cooled to −80° C., and a solutionof 2.23 g (10.0 mmol) of chloro(dimethyl)(2-methyl-1H-inden-7-yl)silanein 15 ml of ether was added dropwise by vigorous stirring for 10 min.This mixture was stirred for 12 h at room temperature, and then 1 ml ofwater was added. The mixture was stirred for 5 min and passed throughshort column with Silica Gel 60 (40-63 um, d 50 mm, l 30 mm). The silicagel layer was additionally washed by 100 ml of ether. The combined elutewas evaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 2.69 g (89%) of1H-inden-1-yl(dimethyl)(2-methyl-1H-inden-7-yl)silane.

Anal. calc. for C₂₄H₂₂Si: C, 83.38; H, 7.33. Found: C, 83.51; H, 7.45.

¹H NMR (CDCl₃): δ 7.48-7.05 (m, 7H, 4,5,6,7-H in indenyl and 4,5,6-H in2-methylindenyl), 6.92 (m, 1H, 3-H in indenyl), 6.57 (m, 1H, 3-H in2-methylindenyl), 6.54 (m, 1H, 2-H in indenyl), 3.88 (m, 1H, 1-H inindenyl), 3.31 (m, 2H, 1,1′-H in 2-methylindenyl), 2.17 (s, 3H, 2-Me in2-methylindenyl), 0.20 (s, 3H, SiMeMe′), 0.16 (s, 3H, SiMeMe′).

¹³C{¹H} NMR (CDCl₃): δ 148.8, 145.9, 145.3, 144.8, 144.3, 135.6, 131.8,129.5, 129.3, 127.1, 125.8, 124.9, 123.6, 123.0, 121.1, 120.9, 45.4,44.2, 16.7, −3.9, −4.3.

Ligand 10

To a solution of 1.30 g (10.0 mmol) of 2-methyl-1H-indene in 90 ml ofether 4.0 ml of 2.5M (10.0 mmol) n-BuLi in hexanes was added at 0° C.This mixture was stirred for 12 h at room temperature, cooled to −50°C., and 449 mg (5.0 mmol) of CuCN was added. The resulting mixture wasstirred for 1 h at −30° C., cooled to −80° C., and a solution of 2.23 g(10.0 mmol) of chloro(dimethyl)(2-methyl-1H-inden-7-yl)silane in 15 mlof ether was added dropwise by vigorous stirring for 10 min. Thismixture was stirred for 12 h at room temperature, and then 1 ml of waterwas added. The mixture was stirred for 5 min and passed through shortcolumn with Silica Gel 60 (40-63 um, d 50 mm, l 30 mm). The silica gellayer was additionally washed by 100 ml of ether. The combined elute wasevaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 2.79 g (88%) ofdimethyl(2-methyl-1H-inden-1-yl)(2-methyl-1H-inden-7-yl)silane.

Anal. calc. for C₂₂H₂₄Si: C, 83.48; H, 7.64. Found: C, 83.20; H, 7.77.

¹H NMR (CDCl₃): δ 7.15-7.37 (m, 5H, 4,5,7-H in 2-methylinden-1-yl and4,6-H in 2-methylinden-4-yl), 6.90-6.99 (m, 2H, 6-H in2-methylinden-1-yl and 5-H in 2-methylinden-4-yl), 6.56 (m, 1H, 3-H in2-methylinden-4-yl), 6.54 (m, 1H, 3-H in 2-methylinden-1-yl), 3.72 (s,1H, 1-H in 2-methylinden-1-yl), 3.24 (m, 2H, 1,1′-H in2-methylinden-4-yl), 2.17 (s, 3H, Me in 2-methylinden-4-yl), 1.98 (s,3H, Me in 2-methylinden-1-yl), 0.24 (s, 3H, SiMeMe′), 0.23 (s, 3H,SiMeMe′).

¹³C{¹H} NMR (CDCl₃): δ 148.9, 147.6, 145.8, 145.2, 145.0, 144.7, 131.9,129.6, 127.0, 125.82, 125.78, 124.8, 123.0, 122.3, 121.1, 119.6, 48.0,44.1, 17.3, 16.7, −3.7, −4.0.

Ligand 11

To a solution of 1.30 g (10.0 mmol) of 3-methyl-1H-indene in 90 ml ofether 4.0 ml of 2.5M (10.0 mmol) n-BuLi in hexanes was added at 0° C.This mixture was stirred for 12 h at room temperature, cooled to −50°C., and 449 mg (5.0 mmol) of CuCN was added. The resulting mixture wasstirred for 1 h at −30° C., cooled to −80° C., and a solution of 2.23 g(10.0 mmol) of chloro(dimethyl)(2-methyl-1H-inden-7-yl)silane in 15 mlof ether was added dropwise by vigorous stirring for 10 min. Thismixture was stirred for 12 h at room temperature, and then 1 ml of waterwas added. The mixture was stirred for 5 min and passed through shortcolumn with Silica Gel 60 (40-63 um, d 50 mm, l 30 mm). The silica gellayer was additionally washed by 100 ml of ether. The combined elute wasevaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 2.85 g (90%) ofdimethyl(2-methyl-1H-inden-7-yl)(3-methyl-1H-inden-1-yl)silane.

Anal. calc. for C₂₂H₂₄Si: C, 83.48; H, 7.64. Found: C, 83.62; H, 7.75.

¹H NMR (CDCl₃): δ 7.16-7.50 (m, 7H, 4,5,6,7-H in 3-methylinden-1-yl and4,5,6-H in 2-methylinden-4-yl), 6.62 (m, 1H, 3-H in 3-methylinden-1-yl),6.32 (m, 1H, 3-H in 2-methylinden-4-yl), 3.84 (m, 1H, 1-H in3-methylinden-1-yl), 3.40 (m, 2H, 1,1′-H in 2-methylinden-4-yl), 2.29(s, 3H, Me in 3-methylinden-1-yl), 2.26 (s, 3H, Me in2-methylinden-4-yl), 0.26 (s, 3H, SiMeMe′), 0.24 (s, 3H, SiMeMe′).

¹³C{¹H} NMR (CDCl₃): δ 148.8, 145.7, 145.4, 145.31, 145.25, 137.4,132.1, 130.5, 129.6, 127.1, 125.8, 124.7, 123.6, 122.9, 121.0, 118.8,44.2, 43.3, 16.7, 12.9, −3.8, −4.2.

Ligand 12

To a solution of 1.72 g (10.0 mmol) of 3-tert-butyl-1H-indene in 90 mlof ether 4.0 ml of 2.5M (10.0 mmol) n-BuLi in hexanes was added at 0° C.This mixture was stirred for 12 h at room temperature, cooled to −50°C., and 449 mg (5.0 mmol) of CuCN was added. The resulting mixture wasstirred for 1 h at −30° C., cooled to −80° C., and a solution of 2.23 g(10.0 mmol) of chloro(dimethyl)(2-methyl-1H-inden-7-yl)silane in 15 mlof ether was added dropwise by vigorous stirring for 10 min. Thismixture was stirred for 12 h at room temperature, and then 1 ml of waterwas added. The mixture was stirred for 5 min and passed through shortcolumn with Silica Gel 60 (40-63 um, d 50 mm, l 30 mm). The silica gellayer was additionally washed by 100 ml of ether. The combined elute wasevaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 2.90 g (81%) of(3-tert-butyl-1H-inden-1-yl)(dimethyl)(2-methyl-1H-inden-7-yl)silane.

Anal. calc. for C₂₅H₃₀Si: C, 83.74; H, 8.43. Found: C, 83.90; H, 8.59.

¹H NMR (CDCl₃): δ 7.68-7.72 (m, 1H, 7-H in 3-tert-butylinden-1-yl),7.10-7.38 (m, 6H, 4,5,6-H in 3-tert-butylinden-1-yl and 4,5,6-H in2-methylinden-4-yl), 6.56 (m, 1H, 3-H in 2-methylinden-1-yl), 6.26 (d,J=2.0 Hz, 1H, 3-H in 3-tert-butylinden-1-yl), 3.75 (m, 1H, 1-H in3-tert-butylinden-1-yl), 3.26 (m, 2H, 1,1′-H in 2-methylinden-4-yl),2.20 (s, 3H, Me), 1.39 (s, 9H, tert-butyl), 0.28 (s, 3H, SiMeMe′), 0.24(s, 3H, SiMeMe′).

¹³C{¹H} NMR (CDCl₃): δ 151.0, 148.9, 146.7, 145.7, 145.2, 143.1, 131.7,129.5, 127.8, 127.0, 125.7, 124.2, 123.4, 123.0, 122.0, 121.0, 44.2,43.0, 33.1, 29.7, 16.7, −3.7, −3.8.

Ligand 13

To a solution of 1.66 g (10.0 mmol) of 9H-fluorene in 90 ml of ether 4.0ml of 2.5M (10.0 mmol) n-BuLi in hexanes was added at 0° C. This mixturewas stirred for 12 h at room temperature, cooled to −50° C., and 449 mg(5.0 mmol) of CuCN was added. The resulting mixture was stirred for 1 hat −30° C., cooled to −80° C., and a solution of 2.23 g (10.0 mmol) ofchloro(dimethyl)(2-methyl-1H-inden-7-yl)silane in 15 ml of ether wasadded dropwise by vigorous stirring for 10 min. This mixture was stirredfor 12 h at room temperature, and then 1 ml of water was added. Themixture was stirred for 5 min and passed through short column withSilica Gel 60 (40-63 um, d 50 mm, l 30 mm). The silica gel layer wasadditionally washed by 100 ml of ether. The combined elute wasevaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 3.24 g (92%) of9H-fluoren-9-yl(dimethyl)(2-methyl-1H-inden-7-yl)silane.

Anal. calc. for C₂₅H₂₄Si: C, 85.17; H, 6.86. Found: C, 85.31; H, 7.03.

¹H NMR (CDCl₃): δ 7.82-7.86 (m, 2H, 4,5-H in fluorenyl), 7.07-7.41 (m,9H, 1,2,3,6,7,8-H in fluorenyl and 4,5,6-H in indenyl), 6.54 (m, 1H, 3-Hin indenyl), 4.18 (m, 1H, 9-H in fluorenyl), 3.18 (m, 1,1′-H inindenyl), 2.15 (m, 3H, 2-Me in indenyl), 0.12 (s, 6H, SiMe₂).

¹³C{¹H} NMR (CDCl₃): δ 149.2, 145.9, 145.3, 145.1, 143.2, 140.5, 131.3,129.9, 127.0, 126.70, 126.67, 125.9, 125.8, 125.3, 125.0, 124.2, 124.1,121.2, 119.9, 119.8, 44.2, 41.6, 36.9, 16.7, −4.2.

Ligand 14

To a solution of 2.61 g (36.2 mmol) of CpLi in 170 ml of TΓΦ a solutionof 8.58 g (36.2 mmol) of 4/7-(2-bromoethyl)-2-methyl-1H-indene in 10 mlof THF was added dropwise by vigorous stirring for 10 min at −80° C.This mixture was stirred for 12 h at room temperature, and then 1 ml ofwater was added. The resulting mixture was evaporated to dryness, and100 ml of water was added to the residue. The crude product wasextracted by 3×50 ml of dichloromethane. The combined organic extractwas dried over Na₂SO₄ and evaporated to dryness. The product wasisolated by flash chromatography using a short column with Silica Gel 60(40-63 um, d 80 mm, l 60 mm; eluent: hexanes. Yield 5.96 g (74%) of amixture of isomeric compounds.

Anal. calc. for C₁₇H₁₈: C, 91.84; H, 8.16. Found: C, 91.69; H, 8.02.

¹H NMR (CDCl₃): δ 6.98-7.33 (m), 6.68 (m), 6.54 (m), 6.32 (m), 6.14 (m),3.67 (m), 3.26-3.40 (m), 2.92-3.07 (m), 2.79 (m), 2.37 (m), 2.23 (m),1.51 (m), 1.35 (m), 0.96 (m).

Ligand 15

To a solution of 4.54 g (35.2 mmol, 90% purity) of 1H-indene in 175 mlof TΓΦ a solution 14.1 ml of 2.5 M (35.3 mmol) of n-BuLi in hexanes wasadded for 5 min at 0° C. This mixture was stirred for 1 h at thistemperature, cooled to −30° C., and a solution of 8.35 g (35.2 mmol) of4/7-(2-bromoethyl)-2-methyl-1H-indene in 10 ml of THF was added dropwiseby vigorous stirring for 10 min at this temperature. This mixture wasstirred for 12 h at room temperature, and then 1 ml of water was added.The resulting mixture was evaporated to dryness, and 100 ml of water wasadded to the residue. The crude product was extracted by 3×50 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyon Silica Gel 60 (40-63 um, d 60 mm, l 300 mm; eluent: hexanes). Yield6.13 g (64%) of 7-[2-(1H-inden-1-yl)ethyl]-2-methyl-1H-indene.

Anal. calc. for C₂₁H₂₀: C, 92.60; H, 7.40. Found: C, 92.45; H, 7.22.

¹H NMR (CDCl₃): δ 7.04-7.54 (m, 7H, 4,5,6,7-H in indenyl and 4,5,6-H in2-methylindenyl), 6.65 (m, 1H, 3-H in indenyl), 6.55 (m, 1H, 3-H in2-methylindenyl), 6.30 (m, 1H, 2-H in indenyl), 3.06-3.41 (m, 7H, 1-H inindenyl and 1,1′-H in 2-methylindenyl and CH₂CH₂), 2.20 (s, 3H, Me).

Ligand 16

To a solution of 4.58 g (35.2 mmol) of 2-methyl-1H-indene in 175 ml ofTΓΦ a solution 14.1 ml of 2.5 M (35.3 mmol) of n-BuLi in hexanes wasadded for 5 min at room temperature. This mixture was stirred for 1 h atthis temperature, cooled to −70° C., and a solution of 8.35 g (35.2mmol) of 4/7-(2-bromoethyl)-2-methyl-1H-indene in 10 ml of THF was addeddropwise by vigorous stirring for 10 min at this temperature. Thismixture was stirred for 12 h at room temperature, and then 1 ml of waterwas added. The resulting mixture was evaporated to dryness, and 100 mlof water was added to the residue. The crude product was extracted by3×50 ml of dichloromethane. The combined organic extract was dried overNa₂SO₄ and evaporated to dryness. The product was isolated by flashchromatography on Silica Gel 60 (40-63 um, d 60 mm, l 300 mm; eluent:hexanes). Yield 5.54 g (55%) of2-methyl-1-[2-(2-methyl-1H-inden-7-yl)ethyl]-1H-indene.

Anal. calc. for C₂₂H₂₂: C, 92.26; H, 7.74. Found: C, 92.01; H, 7.60.

¹H NMR (CDCl₃): δ 7.17-7.61 (m, 7H, 4,5,6,7-H in 2-methylinden-1-yl and4,5,6-H in 2-methylinden-4-yl), 6.67-6.74 (m, 2H, 3-H in both2-methylindenyls), 2.98-3.49 (m, 7H, 1-H in 2-methylinden-1-yl and1,1′-H in 2-methylinden-4-yl and CH₂CH₂), 2.08 (s, 3H, Me in2-methylinden-4-yl), 2.04 (s, 3H, Me in 2-methylinden-1-yl).

Ligand 17

To a solution of 5.85 g (35.2 mmol) of 9H-fluorene in 175 ml of TΓΦ asolution 14.1 ml of 2.5 M (35.3 mmol) of n-BuLi in hexanes was added for5 min at room temperature. This mixture was stirred for 5 h at thistemperature, cooled to −80° C., and a solution of 8.35 g (35.2 mmol) of4/7-(2-bromoethyl)-2-methyl-1H-indene in 10 ml of THF was added dropwiseby vigorous stirring for 10 min at this temperature. This mixture wasstirred for 24 h at room temperature, and then 1 ml of water was added.The resulting mixture was evaporated to dryness, and 100 ml of water wasadded to the residue. The crude product was extracted by 3×50 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyon Silica Gel 60 (40-63 um, d 60 mm, l 300 mm; eluent: hexanes). Yield7.82 g (69%) of a ca. 1 to 1 mixture of9-[2-(2-methyl-1H-inden-7-yl)ethyl]-9H-fluorene (A) and9-[2-(2-methyl-1H-inden-4-yl)ethyl]-9H-fluorene (B).

Anal. calc. for C₂₅H₂₂: C, 93.12; H, 6.88. Found: C, 93.00; H, 6.69.

¹H NMR (CDCl₃): δ 6.98-7.94 (m, 22H, 4,5,6-H in indenyl of A and 5,6,7-Hin indenyl of B and 1,2,3,4,5,6,7,8-H in fluorenyl of both isomers),6.58 (m, 1H, 3-H in indenyl of B), 6.52 (m, 1H, 3-H in indenyl of A),4.22 (m, 2H, 9-H in fluorenyl of both isomers), 3.37 (m, 2H, 1,1′-H inindenyl of A), 3.16 (m, 2H, 1,1′-H in indenyl of B), 2.51 (m, 8H, CH₂CH₂of both isomers), 2.26 (s, 3H, Me of A), 2.24 (s, 3H, Me of B).

Example 4 2-[(2-Methyl-1H-inden-4/7-yl)methyl]indan-1-one

To a solution of 24.5 g (242 mmol) of diisopropylamine in 800 ml of THF96.8 ml of 2.5 M (242 mmol) n-BuLi was added at vigorous stirring for 15min at −80° C. This mixture was stirred for 1 h at −30° C. and thenevaporated to dryness. To a solution of the residue in 800 ml of THF asolution of 32.0 g (242 mmol) of indanone-1 in 200 ml of THF was addeddropwise at vigorous stirring for 20 min at −30° C. The resultingmixture was stirred for 1 h at this temperature, and a solution of 27.0g (121 mmol) of 4/7-(bromomethyl)-2-methyl-1H-indene in 200 ml of THFwas added for 15 min. This mixture was stirred for 24 h at roomtemperature, and 10 ml of water was added. The resulting mixture wasevaporated to dryness. A solution of the residue in 500 ml of ether waswashed by 1 liter of water. The organic layer was separated, and theaqueous layer was washed by 3×200 ml of ether. The product was isolatedby flash chromatography on Silica Gel 60 (40-63 um, d 60 mm, l 400 mm;eluent: hexanes/ether=10/1). Yield 9.30 g (28%).

Anal. calc. for C₂₀H₁₈O: C, 87.56; H, 6.61. Found: C, 87.65; H, 6.73.

¹H NMR (CDCl₃): δ 7.80 (m, 1H), 7.67 (m, 1H), 7.34-7.42 (m, 2H), 7.18(m, 1H), 7.15 (m, 1H), 6.98 (m, 1H), 6.50 (m, 1H), 3.45 (m, 1H), 3.47(m, 1H), 3.28 (s, 2H), 3.19 (m, 1H), 3.08 (m, 1H), 2.85 (m, 1H), 2.64(m, 1H), 2.15-2.17 (m, 6H).

Ligand 18

To a solution of 9.30 g (33.9 mmol) of2-[(2-methyl-1H-inden-4/7-yl)methyl]indan-1-one in 60 ml of THF-methanol(2:1, vol.) 2.78 g (74.1 mmol) of NaBH₄ was added in small portions for2 hours at rt. The mixture was stirred for 12 h at ambient temperatureand then poured on 100 cm³ of ice. The organic layer was separated, theaqueous layer was extracted with 3×300 ml of methyl-tert-butyl ether.The combined extract was dried over K₂CO₃ and evaporated to dryness. Tothe yellowish oil obtained 1250 ml of toluene was added. This toluenesolution was treated with a catalytic amount of TsOH (ca. 280 mg) for 45min at reflux using a Dean-Stark trap. The resulting mixture was passedthrough a short column with Silica Gel 60 (40-63 μm, d 50 mm, l 30 mm).This column was additionally eluted with 200 ml of toluene. The productwas isolated from the combined elute using flash chromatography onSilica Gel 60 (40-63 um, d 60 mm, l 150 mm; eluent: hexanes). Yield 8.23g (94%) of a mixture of isomeric indenes.

Anal. calc. for C₂₀H₁₈: C, 92.98; H, 7.02. Found: C, 92.79; H, 7.11. 1HNMR (CDCl₃): δ 7.17-7.56 (m, 7H), 6.67-6.84 (m, 2H), 3.93-4.12 (m, 2H),3.41-3.51 (m, 4H), 2.32-2.37 (m, 3H).

Complex 1-Zr

To a solution of 2.08 g (10.0 mmol) of ligand 1 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10.0 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×3 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 1.69 g (46%).

Anal. calc. for C₁₆H₁₄Cl₂Zr: C, 52.16; H, 3.83. Found: C, 52.30; H,4.01.

¹H NMR (CD₂Cl₂): δ 7.44 (m, 1H, 4-H in indenyl), 7.23 (m, 1H, 5-H inindenyl), 6.82 (m, 1H, 6-H in indenyl), 6.62 (m, 1H, 3/4-H in Cp), 6.43(m, 1H, 1/3-H in indenyl), 6.28 (m, 1H, 3/1-H in indenyl), 6.16 (m, 1H,2/5-H in Cp), 6.13 (m, 1H, 4/3-H in Cp), 4.69 (m, 1H, 5/2-H in Cp), 4.15(d, J=13.4 Hz, 1H, CHH′), 3.89 (d, J=13.4 Hz, CHH′), 2.35 (s, 3H, Me).

¹³C{¹H} NMR (CD₂Cl₂): δ 145.2, 139.2, 129.4, 129.1, 122.9, 122.8, 120.9,120.1, 118.1, 116.9 (2C), 111.4, 109.4, 99.5, 34.0, 18.0.

Complex 3-Zr

To a solution of 3.02 g (10.0 mmol) of ligand 3 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10.0 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness. The product wasextracted from the residue by 2×10 ml of toluene. The combined extractwas evaporated to dryness, the residue was washed by 2×5 ml of hexanesand dried in vacuum. Yield 951 mg (22%) of pure meso-like complex.

Anal. calc. for C₂₁H₁₈Cl₂Zr: C, 58.32; H, 4.19. Found: C, 58.58; H,4.25.

¹H NMR (CD₂Cl₂): δ 7.37 (m, 1H), 7.24-7.33 (m, 2H), 7.05-6.97 (m, 2H),6.88-6.77 (m, 2H), 6.63 (s, 1H, 3-H in inden-4-yl), 6.38 (d, J=2.2 Hz,1H, 1/3-H in inden-2-yl), 5.96 (d, J=2.2 Hz, 1H, 3/1-H in inden-2-yl),4.50 (d, J=14.1 Hz, 1H), 4.23 (d, J=14.1 Hz, 1H), 2.58 (s, 3H, Me), 2.29(s, 3H, Me).

Complex 3-Hf

To a solution of 3.02 g (10.0 mmol) of ligand 3 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10.0 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas washed by 5×4 ml of cold toluene, 2×10 ml of hexanes, and dried invacuum. Yield 1.09 g (21%) of a ca. 9 to 1 mixture of rac- and meso-likeisomeric complexes.

Anal. calc. for C₂₁H₁₈Cl₂Hf: C, 48.53; H, 3.49. Found: C, 48.60; H,3.57.

¹H NMR (CD₂Cl₂): δ 7.83 (m, 1H), 7.54 (m, 1H), 7.37 (m, 1H), 7.20-7.28(m, 2H), 7.15 (m, 1H), 6.94 (m, 1H), 6.10 (d, J=1.8 Hz, 1H, 1/3-H ininden-2-yl), 6.05 (s, 1H, 3-H in inden-4-yl), 5.89 (d, J=1.8 Hz, 1H,3/1-H in inden-2-yl), 4.63 (d, J=14.4 Hz, 1H), 3.99 (d, J=14.4 Hz, 1H),1.97 (s, 3H, Me), 1.66 (s, 3H, Me).

Complex 4-Zr

To a solution of 3.02 g (10.0 mmol) of ligand 4 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 2×3 ml of cold toluene, 3×10 ml of hexanes,and dried in vacuum. Yield 2.72 g (63%) of a ca. 4 to 3 mixture of rac-and meso-like complexes.

Anal. calc. for C₂₁H₁₈Cl₂Zr: C, 58.32; H, 4.19. Found: C, 58.44; H,4.31.

¹H NMR (CD₂Cl₂): major isomer, δ 7.78-6.76 (m, 7H), 6.28 (m, 1H), 6.10(m, 1H), 4.75 (s, 1H), 4.83 (d, J=13.8 Hz, 1H), 3.99 (d, J=13.8 Hz, 1H),2.23 (s, 3H, Me), 1.97 (s, 3H, Me); minor isomer, δ 7.78-6.76 (m, 7H),6.35 (m, 1H), 6.28 (m, 1H), 6.25 (s, 1H), 4.46 (d, J=14.0 Hz, 1H), 4.32(d, J=14.0 Hz, 1H), 2.47 (s, 3H, Me), 2.28 (s, 3H, Me).

Complex 5-Zr

To a solution of 3.45 g (10.0 mmol) of ligand 5 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas washed by 500 ml of hexanes. Crystals precipitated at −30° C. werecollected, washed by 3×3 ml of cold hexanes, and dried in vacuum. Yield2.66 g (56%) of a ca. 5 to 4 mixture of rac- and meso-like complexes.

Anal. calc. for C₂₄H₂₄Cl₂Zr: C, 60.74; H, 5.10. Found: C, 60.62; H,5.35.

¹H NMR (CD₂Cl₂): major isomer, δ 7.45-6.73 (m, 7H), 6.25 (m, 1H), 6.11(m, 1H), 5.05 (s, 1H), 4.61 (d, J=13.9 Hz, 1H), 4.00 (d, J=13.9 Hz, 1H),1.94 (s, 3H, Me), 1.33 (s, 9H, tert-Bu); minor isomer, 7.45-6.73 (m,7H), 6.55 (s, 1H), 6.41 (m, 1H), 6.34 (m, 1H), 4.48 (d, J=14.1 Hz, 1H),4.29 (d, J=14.1 Hz, 1H), 2.27 (s, 3H, Me), 1.51 (s, 9H, tert-Bu).

Complex 6-Zr

To a solution of 3.08 g (10.0 mmol) of ligand 6 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 100 ml of toluene. Crystals precipitated at−30° C. were collected, washed by 2×5 ml of cold toluene, 2×10 ml ofhexanes, and dried in vacuum. Yield 2.53 g (54%).

Anal. calc. for C₂₄H₁₈Cl₂Zr: C, 61.52; H, 3.87. Found: C, 61.79; H,4.00.

¹H NMR (CD₂Cl₂): δ 8.03-6.97 (m, 11H), 6.22 (m, 1H), 6.16 (m, 1H), 4.98(d, J=14.3 Hz, 1H), 4.42 (d, J=14.3 Hz, 1H), 1.88 (s, 3H, Me).

Complex 7-Zr

To a solution of 2.52 g (10.0 mmol) of ligand 7 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 100 ml of toluene. Crystals precipitated at−30° C. were collected, washed by 3×7 ml of cold toluene, 2×10 ml ofhexanes, and dried in vacuum. Yield 949 mg (23%).

Anal. calc. for C₁₇H₁₈Cl₂SiZr: C, 49.49; H, 4.40. Found: C, 49.66; H,4.52.

¹H NMR (CD₂Cl₂): δ 7.96 (m, 1H, 7-H in indenyl), 7.30 (dd, J=8.3 Hz,J=6.6 Hz, 6-H in indenyl), 7.14 (dd, J=6.6 Hz, J=1.0 Hz, 5-H inindenyl), 6.87 (m, 1H, C₅H₄), 6.61 (m, 1H, C₅H₄), 6.56 (m, 1H, 3-H inindenyl), 6.43 (m, 1H, 1-H in indenyl), 6.32 (m, 1H, C₅H₄), 5.40 (m, 1H,C₅H₄), 2.32 (s, 3H, 2-Me in indenyl), 0.94 (s, 3H, SiMeMe′), 0.65 (s,3H, SiMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 142.5, 136.9, 135.7, 135.3, 128.7, 128.13,128.10, 126.1, 126.0, 120.2, 119.7, 114.2, 110.3, 100.6, 18.4, −1.7,−2.9.

Complex 7-Hf

To a solution of 2.52 g (10.0 mmol) of ligand 7 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×7 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 2.15 g (43%).

Anal. calc. for C₁₇H₁₈Cl₂SiHf: C, 40.85; H, 3.63. Found: C, 41.09; H,3.80.

¹H NMR (CD₂Cl₂): δ 7.55 (m, 1H, 7-H in indenyl), 7.26 (dd, J=7.3 Hz,J=6.4 Hz, 6-H in indenyl), 7.15 (dd, J=6.4 Hz, J=0.8 Hz, 5-H inindenyl), 6.77 (m, 1H, C₅H₄), 6.52 (m, 1H, C₅H₄), 6.37 (m, 1H, 3-H inindenyl), 6.31 (m, 1H, 1-H in indenyl), 6.23 (m, 1H, C₅H₄), 5.29 (m, 1H,C₅H₄), 2.39 (s, 3H, 2-Me in indenyl), 0.93 (s, 3H, SiMeMe′), 0.65 (s,3H, SiMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 141.4, 136.2, 135.3, 128.7, 127.9, 126.4, 126.0,123.9, 122.4, 119.2, 118.2, 113.3, 108.0, 98.4, 18.3, −1.7, −2.7.

Complex 8-Zr

To a solution of 3.09 g (10.0 mmol) of ligand 8 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 1.69 g (36%) of a ca. 8 to 1 mixture of theisomeric complexes.

Anal. calc. for C₂₁H₂₆Cl₂SiZr: C, 53.82; H, 5.59. Found: C, 53.88; H,5.74.

¹H NMR (C₆D₆): major isomer, δ 7.54 (d, J=8.3 Hz, 1H, 7-H in indenyl),7.14 (m, 1H, 6-H in indenyl), 6.86 (d, J=6.6 Hz, 5-H in indenyl), 6.64(m, 1H, C₅H₄), 6.21 (m, 1H, 3-H in indenyl), 6.13 (m, 1H, 1-H inindenyl), 5.99 (m, 1H, C₅H₄), 5.46 (m, 1H, C₅H₄), 2.21 (s, 3H, 2-Me inindenyl), 1.33 (s, 9H, ^(t)Bu), 0.47 (s, 3H, SiMeMe′), 0.26 (s, 3H,SiMeMe′).

Complex 9-Zr

To a solution of 3.02 g (10.0 mmol) of ligand 9 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 20 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 2.04 g (44%) of a ca. 7 to 1 mixture of theisomeric complexes.

Anal. calc. for C₂₁H₂₀Cl₂SiZr: C, 54.52; H, 4.36. Found: C, 54.68; H,4.15.

¹H NMR (CD₂Cl₂): major isomer, δ 7.57 (m, 1H), 7.50 (m, 1H), 7.29 (m,3H), 7.11 (m, 1H), 6.99 (m, 3H), 6.87 (m, 1H), 6.61 (m, 1H), 6.34 (m,1H), 2.28 (s, 3H, 2-Me in 2-methylindenyl), 1.04 (s, 3H, SiMeMe′), 0.92(s, 3H, SiMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 141.4, 135.8, 133.5, 132.9, 129.4, 129.0, 128.6,128.5, 127.9, 127.1, 126.9, 126.0, 123.8, 119.0, 118.3, 110.6, 101.2,100.8, 18.4, −0.4, −2.6.

Complex 9-Hf

To a solution of 3.02 g (10.0 mmol) of ligand 9 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas washed by 3×4 ml of cold toluene, 2×10 ml of hexanes, and dried invacuum. Yield 1.48 g (27%) of one pure isomer.

Anal. calc. for C₂₁H₂₀Cl₂SiHf: C, 45.87; H, 3.67. Found: C, 46.02; H,3.77.

¹H NMR (CD₂Cl₂): δ 7.54 (m, 1H, 5-H in inden-4-yl), 7.45 (m, 1H, 7-H ininden-4-yl), 7.21-7.29 (m, 2H, 5,6-H in inden-1-yl), 7.07 (m, 1H, 6-H ininden-4-yl), 6.96 (m, 1H, 2-H in inden-1-yl), 6.93 (m, 1H, 4-H ininden-1-yl), 6.86 (m, 1H, 7-H in inden-1-yl), 6.85 (m, 1H, 3-H ininden-1-yl), 6.45 (m, 1H, 1-H in inden-4-yl), 6.21 (m, 1H, 3-H ininden-4-yl), 2.36 (s, 3H, 2-Me), 1.03 (s, 3H, SiMeMe′), 0.91 (s, 3H,SiMeMe′).

Complex 10-Zr

To a solution of 3.17 g (10.0 mmol) of ligand 1 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 2.72 g (57%) of one pure isomer.

Anal. calc. for C₂₂H₂₂Cl₂SiZr: C, 55.44; H, 4.65. Found: C, 55.67; H,4.77.

¹H NMR (CD₂Cl₂): δ 7.38-7.47 (m, 3H), 7.26 (m, 1H), 7.08 (m, 1H), 6.86(s, 1H), 6.79 (m, 1H), 6.74 (m, 1H), 6.32 (m, 2H), 2.61 (s, 3H), 2.30(s, 3H), 1.13 (s, 3H), 0.89 (s, 3H).

¹³C{¹H} NMR (CD₂Cl₂): δ 143.7, 135.1, 134.2, 133.4, 130.6, 130.2, 129.4,127.7, 126.6, 126.3, 127.5, 126.7, 126.5, 125.9, 122.9, 111.1, 102.3,101.9, 19.1, 18.5, 2.0, −1.6.

Complex 10-Hf

To a solution of 3.17 g (10.0 mmol) of ligand 10 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 40 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 2.09 g (37%) of a ca. 10 to 1 mixture of theisomeric complexes.

Anal. calc. for C₂₂H₂₂Cl₂SiHf: C, 46.86; H, 3.93. Found: C, 56.81; H,4.15.

¹H NMR (C₆D₆): major isomer, δ 7.32 (m, 2H, 4,7-H in inden-1-yl), 7.06(m, 1H, 5-H in inden-4-yl), 7.01 (m, 1H, 6-H in inden-4-yl), 6.92 (m,1H, 7-H in inden-4-yl), 6.64 (m, 2H, 5,6-H in inden-1-yl), 6.59 (s, 1H,3-H in inden-1-yl), 6.09 (m, 1H, 3-H in inden-4-yl), 5.85 (m, 1H, 1-H ininden-1-yl), 2.27 (s, 3H, 2-Me in inden-1/4-yl), 2.25 (s, 3H, 2-Me ininden-4/1-yl), 0.69 (s, 3H, SiMeMe′), 0.54 (s, 3H, SiMeMe′).

Complex 11-Zr

To a solution of 3.17 g (10.0 mmol) of ligand 11 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 40 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 2.62 g (55%) of one pure isomer.

Anal. calc. for C₂₂H₂₂Cl₂SiZr: C, 55.44; H, 4.65. Found: C, 55.61; H,4.45.

¹H NMR (CD₂Cl₂): δ 7.47 (m, 2H), 7.38 (m, 1H), 7.22-7.31 (m, 2H), 7.10(m, 1H), 6.93 (m, 1H), 6.80 (m, 1H), 6.53-6.56 (m, 2H), 6.32 (m, 1H),2.51 (s, 3H), 2.25 (s, 3H), 1.03 (s, 3H), 0.88 (s, 3H).

Complex 11-Hf

To a solution of 3.17 g (10.0 mmol) of ligand 11 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 40 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 2.65 g (47%) of one pure isomer.

Anal. calc. for C₂₂H₂₂Cl₂SiHf: C, 46.86; H, 3.93. Found: C, 46.08; H,3.10.

¹H NMR (CD₂Cl₂): δ 7.43 (m, 1H, 7-H in inden-4-yl), 7.36 (m, 1H, 4/7-Hin inden-1-yl), 7.21-7.33 (m, 2H, 5,6-H in inden-4-yl), 7.07 (m, 1H,5/6-H in inden-1-yl), 6.88 (m, 1H, 6/5-H in inden-1-yl), 6.79 (m, 1H,7/4-H in inden-1-yl), 6.52 (s, 1H, 2-H in inden-1-yl), 6.40 (m, 1H, 3-Hin inden-4-yl), 6.21 (m, 1H, 1-H in inden-1-yl), 2.58 (s, 3H, 2-Me ininden-1/4-yl), 2.33 (s, 3H, 2-Me in inden-4/1-yl), 1.01 (s, 3H,SiMeMe′), 0.87 (s, 3H, SiMeMe′).

Complex 12-Zr

To a solution of 3.59 g (10.0 mmol) of ligand 12 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 40 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 1.38 g (29%) of a ca. 3.7 to 1 mixture of theisomeric complexes.

Anal. calc. for C₂₅H₂₈Cl₂SiZr: C, 57.89; H, 5.44. Found: C, 58.11; H,5.60.

¹H NMR (CD₂Cl₂): major isomer, δ 7.90 (m, 2H), 7.55 (m, 1H), 7.27-7.34(m, 3H), 7.19 (m, 1H), 6.61 (m, 1H), 6.18 (m, 1H), 5.56 (m, 1H), 1.82(s, 3H), 1.37 (s, 9H), 1.18 (s, 3H), 0.68 (s, 3H).

Complex 12-Hf

To a solution of 3.59 g (10.0 mmol) of ligand 12 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 40 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 1.58 g (26%) of a ca. 14 to 3 mixture of theisomeric complexes.

Anal. calc. for C₂₅H₂₈Cl₂SiHf: C, 49.55; H, 4.66. Found: C, 49.71; H,4.79.

¹H NMR (CD₂Cl₂): major isomer, δ 7.81-7.95 (m, 2H, 4,7-H in inden-1-yl),7.52 (m, 1H, 7-H in inden-4-yl), 7.17-7.30 (m, 4H, 5,6-H in inden-1-yland 5,6-H in inden-4-yl), 6.43 (m, 1H, 3-H in inden-4-yl), 6.09 (m, 1H,1-H in inden-4-yl), 5.50 (s, 1H, 2-H in inden-1-yl), 1.89 (s, 3H, 2-Me),1.36 (s, 9H, ^(t)Bu), 1.17 (s, 3H, SiMeMe′), 0.68 (s, 3H, SiMeMe′).

Complex 13-Zr

To a solution of 3.53 g (10.0 mmol) of ligand 13 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 80 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×2 ml of cold toluene, 2×7 ml of hexanes,and dried in vacuum. Yield 3.08 g (60%).

Anal. calc. for C₂₅H₂₂Cl₂SiZr: C, 58.57; H, 4.33. Found: C, 58.79; H,4.41.

¹H NMR (C₆D₆): δ 7.85 (m, 1H), 7.70 (m, 1H), 7.59 (m, 1H), 7.32-7.37 (m,3H), 7.18 (dd, J=6.5 Hz, J=1.0 Hz, 1H, 5-H in indenyl), 7.13 (m, 1H),6.99 (dd, J=8.5 Hz, J=6.5 Hz, 1H, 6-H in indenyl), 6.90 (ddd, J=8.7 Hz,J=6.7 Hz, J=1.0 Hz, 1H), 6.83 (m, 1H, 7-H in indenyl), 6.32 (m, 1H, 1-Hin indenyl), 5.98 (m, 1H, 3-H in indenyl), 1.83 (s, 3H, 2-Me inindenyl), 0.90 (s, 3H, SiMeMe′), 0.57 (s, 3H, SiMeMe′).

Complex 14-Zr

To a solution of 2.22 g (10.0 mmol) of ligand 14 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 20 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 2×2 ml of cold toluene, 3×10 ml of hexanes,and dried in vacuum. Yield 1.22 g (32%).

Anal. calc. for C₁₇H₁₆Cl₂Zr: C, 53.39; H, 4.22. Found: C, 53.52; H,4.06.

¹H NMR (CD₂Cl₂): δ 7.54 (m, 1H, 7-H in indenyl), 7.16 (dd, J=8.3 Hz,J=7.1 Hz, 6-H in indenyl), 7.05 (m, 1H, 5-H in indenyl), 6.54 (m, 1H, CHin Cp), 6.39 (m, 1H, 1/3-H in indenyl), 6.23 (m, 1H, CH in Cp), 6.17 (m,1H, 3/1-H in indenyl), 6.12 (m, 1H, CH in Cp), 4.62 (m, 1H, CH in Cp),3.63 (m, 1H, CHH′), 3.45 (m, 1H, CHH′), 3.21 (m, 1H, CHH′), 3.06 (m, 1H,CHH′), 2.31 (s, 3H, 2-Me in indenyl).

Complex 14-Hf

To a solution of 2.22 g (10.0 mmol) of ligand 14 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness. The residue waswashed by 50 ml of hexanes, and then the product was extracted by 3×5 mlof ether. Crystals precipitated at −30° C. were collected and dried invacuum. Yield 1.60 g (34%).

Anal. calc. for C₁₇H₁₆Cl₂Hf: C, 43.47; H, 3.43. Found: C, 43.22; H,3.49.

¹H NMR (CD₂Cl₂): δ 7.52 (m, 1H, 7-H in indenyl), 7.13 (dd, J=8.3 Hz,J=6.8 Hz, 6-H in indenyl), 7.03 (m, 1H, 5-H in indenyl), 6.42 (m, 1H, CHin Cp), 6.26 (m, 1H, 1/3-H in indenyl), 6.14 (m, 1H, CH in Cp), 6.00 (m,1H, 3/1-H in indenyl), 5.95 (m, 1H, CH in Cp), 4.47 (m, 1H, CH in Cp),3.68 (m, 1H, CHH′), 3.52 (m, 1H, CHH′), 3.24 (m, 2H, CHH′CHH′), 2.39 (s,3H, 2-Me in indenyl).

Complex 15-Zr

To a solution of 2.72 g (10.0 mmol) of ligand 15 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 2×3 ml of cold toluene, 3×10 ml of hexanes,and dried in vacuum. Yield 1.77 g (41%) of one pure isomer.

Anal. calc. for C₂₁H₁₈Cl₂Zr: C, 58.32; H, 4.19. Found: C, 58.47; H,4.34.

¹H NMR (CD₂Cl₂): δ 7.71 (m, 1H), 7.09-7.44 (m, 5H), 6.87 (m, 1H), 6.54(m, 1H), 6.22 (m, 1H), 5.70 (m, 1H), 4.49 (m, 1H), 3.46 (m, 1H, CHH′),3.28 (m, 1H, CHH′), 2.82 (m, 1H, CHH′), 2.66 (m, 1H, CHH′), 2.04 (s, 3H,2-Me in indenyl).

Complex 16-Zr

To a solution of 2.86 g (10.0 mmol) of ligand 16 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 15 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 2×5 ml of cold toluene, 2×20 ml of hexanes,and dried in vacuum. Yield 804 mg (18%) of a ca. 2 to 1 mixture of theisomeric complexes.

Anal. calc. for C₂₂H₂₀Cl₂Zr: C, 59.18; H, 4.51. Found: C, 59.40; H,4.65.

¹H NMR (C₆D₆): major isomer, δ 7.62 (m, 1H), 7.49 (m, 1H), 7.33 (m, 1H),7.01 (m, 1H), 6.95 (m, 1H), 6.90 (m, 1H), 6.66 (m, 1H), 6.02 (m, 1H),5.98 (m, 1H), 5.72 (m, 1H), 3.21 (m, 1H, CHH′), 2.74 (m, 1H, CHH′), 2.68(m, 1H, CHH′), 2.35 (m, 1H, CHH′), 1.74 (s, 3H, Me), 1.54 (s, 3H, Me).

Complex 17-Zr

To a solution of 3.22 g (10.0 mmol) of ligand 17 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 20 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 2×3 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 3.33 g (69%).

Anal. calc. for C₂₅H₂₀Cl₂Zr: C, 62.22; H, 4.18. Found: C, 62.37; H,4.07.

¹H NMR (CD₂Cl₂): δ 8.26 (m, 1H), 8.09 (m, 1H), 8.00 (m, 1H), 7.61 (m,2H), 7.53 (m, 1H), 7.40 (m, 1H), 7.28 (m, 3H), 7.13 (m, 1H), 6.42 (m,1H, 3-H in indenyl), 6.24 (m, 1H, 1-H in indenyl), 4.04 (m, 2H,CHH′CHH′), 3.57 (m, 2H, CHH′CHH′), 1.98 (s, 3H, 2-Me in indenyl).

Complex 18-Zr

To a solution of 2.58 g (10.0 mmol) of ligand 18 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was washed by 3×5 ml of toluene, 3×2 ml ofdichloromethane, 2×10 ml of hexanes, and dried in vacuum. Yield 1.05 g(25%).

Anal. calc. for C₂₀H₁₆Cl₂Zr: C, 57.40; H, 3.85. Found: C, 57.46; H,4.04.

¹H NMR (CD₂Cl₂): δ 7.36-7.45 (m, 3H), 7.25 (m, 2H), 7.10 (m, 1H), 6.90(m, 1H), 6.60 (m, 1H), 6.39 (m, 1H), 6.28 (m, 1H), 4.67 (m, 1H), 4.27(d, J=13.4 Hz, 1H, CHH′), 3.94 (d, J=13.4 Hz, 1H, CHH′), 2.34 (s, 3H,Me).

¹³C{¹H} NMR (CD₂Cl₂): δ 139.6, 135.0, 134.8, 129.4, 127.8, 126.6, 126.3,125.9, 123.1, 122.0, 119.7, 110.5, 108.5, 102.5, 101.5, 35.1, 18.3.

Complex 18-Hf

To a solution of 2.58 g (10.0 mmol) of ligand 18 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 40 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×5 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 1.57 g (31%).

Anal. calc. for C₂₀H₁₆Cl₂Hf: C, 47.50; H, 3.19. Found: C, 47.69; H,3.30.

¹H NMR (CD₂Cl₂): δ 7.41 (m, 1H), 7.37 (m, 1H), 7.34 (m, 1H), 7.21 (m,2H), 7.06 (m, 1H), 6.91 (m, 1H), 6.37 (m, 1H), 6.28 (m, 1H), 6.16 (m,1H), 4.53 (m, 1H), 4.29 (d, J=13.5 Hz, 1H, CHH′), 4.07 (d, J=13.5 Hz,1H, CHH′), 2.41 (s, 3H, 2-Me in indenyl).

Example 52-[2-(1-Methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-ol

To 2.26 g (93.0 mmol) of magnesium turnings in 20 ml of THF a solutionof 16.7 g (62.0 mmol) of 4-(2-bromoethyl)-1-methoxy-2-methylindane in 80ml of THF was added dropwise at reflux. The resulting mixture wasadditionally refluxed for 1 h, and then this Grignard reagent wastitrated. To a suspension of 10.9 g (44.1 mmol) of anhydrous CeCl₃ in160 ml of THF 100 ml (44.1 mmol) of 0.441 M solution of the Grignardreagent was added at vigorous stirring for 15 min at 0° C., and then thereaction mixture was stirred at this temperature for 1.5 h. Further on,5.83 g (44.1 mmol) of indanone-2 was added at 0° C. This mixture wasstirred overnight at room temperature, and then 300 ml of 10% aceticacid was added. The product was extracted by 3×100 ml of ether. Thecombined extract was washed by brain and aqueous Na₂CO₃. The organiclayer was separated, dried over Na₂SO₄, and evaporated to dryness. Thetitle product was isolated by flash chromatography on Silica Gel 60(40-63 um, d 50 mm, l 300 mm, eluent: hexanes/ether=3/1). Yield 10.7 g(75%) of a one diastereomer (as the starting material was one purediastereomer).

Anal. calc. for C₂₂H₂₆O₂: C, 81.95; H, 8.13. Found: C, 82.29; H, 8.32.

¹H NMR (CDCl₃): δ 7.12-7.26 (m, 7H, 4,5,6,7-H in indan-2-ol and 5,6,7-Hin methoxyindane), 4.42 (d, J=4.1 Hz, 1H, CHOMe), 3.46 (s, 3H, OMe),3.23 (dd, J=15.7 Hz, J=7.6 Hz, 1H, CHH′CHMe), 3.12 (d, J=16.2 Hz, 2H,CHH′ in indan-2-ol), 3.00 (d, J=16.2 Hz, 2H, CHH′ in indan-2-ol), 2.80(m, 2H, HOCCH₂CH₂), 2.52 (m, 1H, CHMe), 2.43 (dd, J=15.7 Hz, J=5.1 Hz,1H, CHH′CHMe), 2.03 (m, 2H, HOCCH₂), 1.83 (br.s, 1H, OH), 1.18 (d, J=7.0Hz, 3H, CHMe).

Ligand 19

To a hot (110° C.) solution of 4.00 g (12.4 mmol) of2-[2-(1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-ol in730 ml of toluene 0.37 g of TsOH was added. This mixture was refluxedwith Dean-Stark trap for 35 min, and then 0.75 g of TsOH was added. Theresulting mixture was refluxed for 35 min and then passed through thelayer of Silica Gel 60 (40-63 um, d 80 mm, l 50 mm). The Silica Gellayer was additionally washed by 500 ml of toluene. The combined organicextract was evaporated to dryness. The product was isolated by flashchromatography using a short column with Silica Gel 60 (40-63 um, d 80mm, 150 mm; eluent: hexanes). Yield 2.87 g (85%) of7-[2-(1H-inden-2-yl)ethyl]-2-methyl-1H-indene.

Anal. calc. for C₂₄H₂₀: C, 92.60; H, 7.40. Found: C, 92.89; H, 7.64.

¹H NMR (CDCl₃): δ 7.39 (m, 1H, 4-H in inden-7-yl), 7.28 (m, 2H, 5,6-H ininden-2-yl), 7.25 (m, 1H, 5-H in inden-7-yl), 7.13 (m, 2H, 4,7-H ininden-2-yl), 6.99 (m, 1H, 6-H in inden-7-yl), 6.51 (m, 1H, 3-H ininden-7-yl), 3.36 (m, 2H, 1,1′-H in inden-2-yl), 3.27 (m, 2H, 1,1′-H ininden-7-yl), 2.99 (m, 2H, inden-2-yl-CH₂CH₂-inden-7-yl), 2.85 (m, 2H,inden-2-yl-CH₂CH₂-inden-7-yl), 2.17 (m, 3H, Me).

Complex 19-Zr

To a solution of 2.72 g (10.0 mmol) of ligand 19 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10.0 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×3 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 2.25 g (52%).

Anal. calc. for C₁₆H₁₄Cl₂Zr: C, 58.32; H, 4.19. Found: C, 58.30; H,4.32.

¹H NMR (CD₂Cl₂): δ 7.61 (m, 1H), 7.47 (m, 1H), 7.22 (m, 1H), 7.12-7.17(m, 4H), 6.33 (m, 1H), 6.18 (m, 1H), 6.14 (m, 1H), 4.46 (m, 1H), 3.76(m, 1H), 3.60 (m, 1H), 3.36 (m, 1H), 3.26 (m, 1H), 2.30 (m, 3H).

¹³C{¹H} NMR (CD₂Cl₂): δ 143.3, 137.7, 136.9, 131.3, 131.0, 130.5, 129.7,128.0, 126.91, 126.87, 126.63, 126.58, 126.2, 124.1, 111.6, 107.3,103.3, 101.2, 30.6, 28.5, 18.7.

Complex 19-Hf

To a solution of 2.72 g (10.0 mmol) of ligand 19 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10.0 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×3 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 4.05 g (78%).

Anal. calc. for C₁₆H₁₄Cl₂Hf: C, 48.53; H, 3.49. Found: C, 48.77; H,3.60.

¹H NMR (CD₂Cl₂): δ 7.58 (m, 1H), 7.46 (m, 1H), 7.19 (m, 1H), 7.08-7.15(m, 4H), 6.21 (m, 1H), 6.05 (m, 1H), 5.98 (m, 1H), 4.34 (m, 1H), 3.81(m, 1H), 3.67 (m, 1H), 3.50 (m, 1H), 3.35 (m, 1H), 2.40 (m, 3H).

¹³C{¹H} NMR (CD₂Cl₂): δ 142.3, 137.8, 136.8, 131.1, 130.5, 129.7, 129.4,127.8, 127.0, 126.7, 126.5, 126.3, 125.7, 124.0, 109.2, 103.6, 100.9,98.4, 30.6, 28.2, 18.6.

Example 62-[(1-Methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)methylene]-5-methylindan-1-one

To sodium methylate obtained from 157 mg (6.83 mmol) of sodium and 60 mlof methanol 4.70 g (24.7 mmol) of1-methoxy-2-methylindane-4-carbaldehyde was added at 0° C. The resultingmixture was stirred for 5 min at this temperature, and 3.32 g (22.7mmol) of 6-methylindan-1-one was added. This mixture was stirredovernight at room temperature, and 5% HCl was added to pH 5. Theprecipitate formed was filtered off and washed by 3×10 ml of coldmethanol. Yield 6.87 g (95%) of a ca. 1 to 1 mixture of twodiastereomers.

Anal. calc. for C₂₂H₂₂O₂: C, 82.99; H, 6.96. Found: C, 83.31; H, 7.23.

¹H NMR (CDCl₃): δ 7.79 (d, J=7.8 Hz, 2H, 7-H in indan-2-diyl of bothisomers), 7.73 (m, 1H, CH═ of the isomer A), 7.71 (m, 1H, CH═ of theisomer B), 7.63 (m, 2H, 7-H in indan-4-yl of both isomers), 7.40 (m, 2H,6-H in indan-4-yl of both isomers), 7.32 (m, 2H, 5-H in indan-4-yl ofboth isomers), 7.31 (s, 2H, 4-H in indan-2-diyl of both isomers), 7.22(d, J=7.8 Hz, 2H, 7-H in indan-2-diyl of both isomers), 4.57 (d, J=5.8Hz, 1H, CHOMe of the isomer A), 4.42 (d, J=4.1 Hz, 1H, CHOMe of theisomer B), 3.96 (m, 4H, CH₂ in indan-2-diyl of both isomers), 3.47 (s,3H, OMe of the isomer B), 3.43 (s, 3H, OMe of the isomer A), 3.41 (dd,J=16.2 Hz, J=7.6 Hz, 1H, CHH′ in indan-4-yl of the isomer B), 3.12 (dd,J=16.0 Hz, J=7.3 Hz, 1H, CHH′ in indan-4-yl of the isomer A), 2.86 (dd,J=16.0 Hz, J=6.3 Hz, 1H, CHH′ in indan-4-yl of the isomer A), 2.67 (m,1H, CHMe in indan-4-yl of the isomer A), 2.63 (dd, J=16.2 Hz, J=5.1 Hz,1H, CHH′ in indan-4-yl of the isomer B), 2.65 (m, 1H, CHMe in indan-4-ylof the isomer B), 2.46 (s, 6H, 6-Me in indan-2-diyl of both isomers),1.18 (d, J=7.1 Hz, 3H, 2-Me in indan-4-yl of the isomer B), 1.10 (d,J=6.8 Hz, 3H, 2-Me in indan-4-yl of the isomer A).

2-[(1-Methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)methyl]-5-methylindan-1-ol

To a solution of 28.1 g (88.3 mmol) of2-[(1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)methylene]-5-methylindan-1-onein 1800 ml of a mixture of THF and methanol (1 to 8, vol.) 4.50 g (119mmol) of NaBH₄ was added by small portions at vigorous stirring at 0° C.This mixture was stirred for 1 h at room temperature, 65.6 g (0.276 mol)of CoCl₂(H₂O) was added. The resulting mixture was stirred for 15 min atroom temperature, and then 12.6 g (333 mmol) of NaBH₄ was added by smallportions for ca. 15 min. This mixture was stirred for 2 h at roomtemperature and then evaporated to dryness. To the residue 1000 ml ofwarm water and 300 ml of dichloromethane were added. The organic layerwas separated, the aqueous layer was extracted with 3×300 ml ofdihloromethane. The combined extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyon Silica Gel 60 (40-63 um, d 50 mm, l 300 mm, eluent: hexanes/ethylacetate=3/1). Yield 22.8 g (80%).

Anal. calc. for C₂₂H₂₆O₂: C, 81.95; H, 8.13. Found: C, 82.29; H, 8.30.

¹H NMR (CDCl₃): δ 7.26 (m, 1H, 7-H in inden-4-yl), 7.24 (m, 1H, 6-H ininden-2-yl), 7.19 (m, 6-H in inden-4-yl), 7.15 (m, 1H, 5-H ininden-4-yl), 7.04 (m, 1H, 7-H in inden-2-yl), 6.98 (m, 1H, 4-H ininden-2-yl), 4.89 (m, 1H, CHOH), 4.39 (d, J=4.1 Hz, 1H, CHOMe), 3.46 (s,3H, OMe), 3.20 (dd, J=15.6 Hz, J=7.4 Hz, 1H, CHH′CHMe in inden-4-yl),2.93-3.02 (m, 2H, CHH′CHCH₂ in inden-2-yl and CHMe in inden-4-yl), 2.72(dd, J=13.7 Hz, J=8.4 Hz, 1H, CHH′CHCH₂ in inden-2-yl), 2.46-2.56 (m,3H, CH₂CH(CHOH)CH₂), 2.42 (dd, J=15.6 Hz, J=5.1 Hz, 1H, CHH′CHMe ininden-4-yl), 2.32 (m, 3H, 5-Me in inden-2-yl), 1.61 (br.d, J=5.4 Hz, 1H,OH), 1.15 (d, J=6.9 Hz, 3H, CHMe).

Ligand 20

To a hot (110° C.) solution of 7.20 g (22.3 mmol) of2-[(1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)methyl]-5-methylindan-1-olin 1300 ml of toluene 0.67 g of TsOH was added. This mixture wasrefluxed with Dean-Stark trap for 10 min and then passed through thelayer of Silica Gel 60 (40-63 um, d 80 mm, l 50 mm). The Silica Gellayer was additionally washed by 500 ml of toluene. The combined organicextract was evaporated to dryness. The product was isolated by flashchromatography using a short column with Silica Gel 60 (40-63 um, d 80mm, 150 mm; eluent: hexanes). Yield 5.47 g (90%).

Anal. calc. for C₂₁H₂₀: C, 92.60; H, 7.40. Found: C, 92.49; H, 7.57.

¹H NMR (CDCl₃): δ 7.25 (m, 1H), 7.20-7.23 (m, 3H), 7.19 (s, 1H), 7.09(m, 1H), 7.03 (m, 1H), 6.55 (m, 1H), 6.51 (m, 1H), 3.98 (s, 2H), 3.30(m, 2H), 3.28 (m, 2H), 2.41 (s, 3H), 2.20 (m, 3H).

Complex 20-Zr

To a solution of 2.72 g (10.0 mmol) of ligand 20 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 3.77 g (10.0 mmol) of ZrCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×3 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 2.12 g (49%) of a ca. 4 to 1 mixture of twoisomeric complexes.

Anal. calc. for C₁₆H₁₄Cl₂Zr: C, 58.32; H, 4.19. Found: C, 58.37; H,4.41.

¹H NMR (CD₂Cl₂): major isomer, δ 7.37 (d, J=8.7 Hz, 1H, 7-H ininden-2-yl), 7.29 (d, J=8.7 Hz, 1H, 6-H in inden-2-yl), 7.24 (dd, J=8.6Hz, J=6.8 Hz, 1H, 6-H in inden-4-yl), 7.21 (s, 1H, d, J=8.6 Hz, 1H, 4-Hin inden-2-yl), 6.96 (dd, J=8.6 Hz, J=1.3 Hz, 1H, 5-H in inden-4-yl),6.86 (d, J=6.8 Hz, 1H, 7-H in inden-4-yl), 6.58 (d, J=2.0 Hz, 1H, 3-H ininden-4-yl), 6.29 (d, J=2.5 Hz, 1H, 1/3-H in inden-2-yl), 6.27 (d, J=2.0Hz, 1H, 1-H in inden-4-yl), 4.60 (d, J=2.5 Hz, 1H, 3/1-H in inden-2-yl),4.24 (d, J=13.4 Hz, 1H, CHH′), 3.91 (d, J=13.4 Hz, 1H, CHH′), 2.42 (s,3H, 2-Me in inden-4-yl), 2.33 (s, 3H, 5-Me in inden-2-yl).

¹³C{¹H} NMR (CD₂Cl₂): δ 143.3, 139.4, 139.3, 138.5, 135.1, 134.1, 132.0,130.6, 129.4, 129.3, 125.9, 124.0, 123.1, 119.6, 110.4, 108.3, 102.2,101.4, 35.1, 23.2, 18.2.

Complex 20-Hf

To a solution of 2.72 g (10.0 mmol) of ligand 20 in 200 ml of ether 8.0ml of 2.5 M (20 mmol) of n-BuLi in hexanes was added by vigorousstirring for 5 min at room temperature. This mixture was stirred for 12h, then cooled to −30° C., and 4.64 g (10.0 mmol) of HfCl₄(THF)₂. Theresulting mixture was stirred for 24 h at room temperature and thenevaporated to dryness. A mixture of the residue obtained and 200 ml oftoluene was stirred for 6 h at 80° C. and then filtered through glassfrit (G4). The precipitate was additionally washed by 3×50 ml of hottoluene. The combined extract was evaporated to dryness, and the residuewas re-crystallized from 30 ml of toluene. Crystals precipitated at −30°C. were collected, washed by 3×3 ml of cold toluene, 2×10 ml of hexanes,and dried in vacuum. Yield 2.12 g (49%) a ca. 2 to 1 mixture of twoisomeric complexes.

Anal. calc. for C₁₆H₁₄Cl₂Zr: C, 48.53; H, 3.49. Found: C, 48.70; H,3.61.

¹H NMR (CD₂Cl₂): major isomer, δ 7.36 (d, J=8.5 Hz, 1H, 7-H ininden-2-yl), 7.24 (d, J=8.5 Hz, 1H, 6-H in inden-2-yl), 7.17-7.23 (m,2H, 6-H in inden-4-yl and 4-H in inden-2-yl), 6.93 (dd, J=8.8 Hz, J=1.3Hz, 1H, 5-H in inden-4-yl), 6.87 (d, J=6.6 Hz, 1H, 7-H in inden-4-yl),6.36 (d, J=2.0 Hz, 1H, 3-H in inden-4-yl), 6.18 (d, J=2.5 Hz, 1H, 1/3-Hin inden-2-yl), 6.15 (d, J=2.0 Hz, 1H, 1-H in inden-4-yl), 4.41 (d,J=2.5 Hz, 1H, 3/1-H in inden-2-yl), 4.28 (d, J=13.4 Hz, 1H, CHH′), 4.24(d, J=13.4 Hz, 1H, CHH′), 2.46 (s, 3H, 2-Me in inden-4-yl), 2.40 (s, 3H,5-Me in inden-2-yl).

¹³C{¹H} NMR (CD₂Cl₂): δ 142.2, 140.3, 138.4, 136.4, 134.4, 133.8, 131.0,130.6, 129.1, 129.0, 126.1, 123.7, 123.1, 119.4, 108.2, 104.8, 100.5,98.6, 35.1, 23.1, 18.1.

Example 7

2-Methyl-4-bromo-6-tert-butylindanone-1 was obtained as described in theliterature [Resconi, L.; Nifant'ev, I. E.; Ivchenko, P. V.; Bagrov, V.;Focante, F.; Moscardi, G. Int. Pat. Appl. WO2007/107448 A1].

4/7-Bromo-6/5-tert-butyl-2-methyl-1H-indene

To a solution of 146 g (0.52 mol) of 4-bromo-2-methyl-1-indanone in 950ml of THF-methanol (2:1, vol.) 38.3 g (1.02 mol) of NaBH₄ was added insmall portions over 2 h at 0° C. The mixture was stirred overnight atambient temperature. The resulting mixture was poured onto 1000 cm³ ofice and acidified with 10% HCl to pH 4. The organic layer was separated;the aqueous layer was extracted with 3×300 ml of methyl-tert-butylether. This combined extract was dried over K₂CO₃ and evaporated todryness, and 1500 ml of toluene were added to the residue. This toluenesolution was treated with a catalytic amount of ^(p)TolSO₃H*H₂O (ca. 2g) for 2 h at reflux. Then this mixture was cooled to room temperatureand passed through a short column with Silica Gel 60 (40-63 um, d 60 mm,l 40 mm). This column was additionally eluted with 250 ml of toluene.The combined extract was evaporated to dryness. Fractional distillationgave a mixture of the title indene, b.p. 124-128° C./5 mm Hg. Yield 83 g(83%) of colorless solid.

Anal. calc. for C₁₄H₁₇Br: C, 63.41; H, 6.46. Found: C, 63.61; H, 6.61.

¹H NMR (CDCl₃) of 7-bromo-2-methyl-5-tert-buthyl-1H-indene: δ 7.31 (m,J=1H, 6-H), 7.28 (m, 1H, 4-H), 6.53 (m, 1H, 3-H), 3.30 (m, 2H, 1,1′-H),2.21 (s, 3H, 2-Me), 1.39 (s, 9H, 5-C(CH₃)₃).

¹³C{¹H} NMR (CDCl₃) of 7-bromo-2-methyl-5-tert-buthyl-1H-indene: δ152.2, 147.2, 146.8, 140.4, 127.4, 123.9, 118.1, 116.1, 43.9, 34.8,31.6, 16.8.

(6/5-tert-Butyl-2-methyl-1H-inden-4/7-yl)(chloro)dimethylsilane

To 1.63 g (67 mmol) of magnesium turnings (activated by 0.2 ml of1,2-dibromoethane for 10 min) in 50 ml of THF a solution of 14.6 g (55mmol) of 2-methyl-5-tert-buthyl-7-bromoindene in 350 ml of THF was addeddropwise at vigorous stirring for ca. 40 min. This mixture wasadditionally refluxed for 1 h, and then cooled to room temperature. TheGrignard reagent obtained was added dropwise at vigorous stirring to asolution of 21.4 g (166 mmol) of dichlorodimethylsilane in 50 ml of THFfor 1 h at room temperature. The resulting mixture was stirred for 12 hand then evaporated to dryness. The residue was dissolved in 100 ml ofether, and the solution obtained was filtered through glass frit (G3).The precipitate was additionally washed by 3×50 ml of ether. Thecombined ether solution was evaporated to dryness, and the residue wasdistilled in vacuum, by 130-132° C./1 mm Hg. Yield 11.0 Γ (72%).

Anal. calc. for C₁₆H₂₃ClSi: C, 68.91; H, 8.31. Found: C, 69.07; H, 8.46.

¹H NMR (CD₂Cl₂): δ 7.42 (m, 1H, 6-H), 7.38 (m, 1H, 4-H), 6.50 (m, 1H,3-H), 3.43 (br.s, 2H, 1,1′-H), 2.19 (br.s, 3H, 2-Me), 1.36 (s, 9H,5-C(CH₃)₃), 0.86 (s, 6H, Me₂SiCl).

(6/5-tert-Butyl-2-methyl-1H-inden-4/7-yl)(cyclopenta-2,4-dien-1-yl)dimethylsilane

To a solution of 971 mg (13.5 mmol) of CpLi in 100 ml of THF a solutionof 3.77 g (13.5 mmol) ofchloro(dimethyl)(2-methyl-5-tert-buthyl-1H-inden-7-yl)silane in 10 ml ofTHF was added dropwise by vigorous stirring for 5 min at −80° C. Thismixture was additionally stirred for 1 h at room temperature, and 1 mlof water was added. The mixture was evaporated to dryness, and 100 ml ofwater was added to the residue. The crude product was extracted with3×50 ml of dichloromethane. The combined organic extract was dried overNa₂SO₄ and evaporated to dryness. The product was isolated from theresidue by flash chromatography using a short column with Silica Gel 60(40-63 um, d 60 mm, l 50 mm; eluent: hexanes). Yield 3.85 g (86%) ofpurecyclopenta-2,4-dien-1-yl(dimethyl)(2-methyl-5-tert-buthyl-1H-inden-7-yl)silane.

Anal. calc. for C₂₁H₂₈Si: C, 81.75; H, 9.15. Found: C, 81.52; H, 9.09.

¹H NMR (CDCl₃): δ 7.35-7.39 (m, 2H, 4,6-H in indenyl), 6.65 (br.s, 2H,3,4-H in Cp), 6.50-6.56 (m, 3H, 3-H in indenyl and 2,5-H in Cp), 3.78(br.s, 1H, 1-H in Cp), 3.36 (s, 2H, 1,1′-H in indenyl), 2.19 (s, 3H,2-Me in indenyl), 1.39 (s, 9H, C(CH₃)₃ in indenyl), 0.25 (s, 6H, SiMe₂).

¹³C{¹H} NMR (CDCl₃): δ 148.6, 145.9, 145.7, 145.4, 133.5 (br.), 131.7,130.6 (br.), 127.3, 126.2, 118.3, 51.1, 43.7, 31.6, 29.7, 16.8, −3.5.

(6/5-tert-Butyl-2-methyl-1H-inden-4/7-yl)(dimethyl)(3-methyl-1H-inden-1-yl)silane

To a solution of 1.30 g (10.0 mmol) of 3-methyl-1H-indene in 90 ml ofether 4.0 ml of 2.5M (10.0 mmol) n-BuLi in hexanes was added at 0° C.This mixture was stirred for 12 h at room temperature, cooled to −50°C., and 449 mg (5.0 mmol) of CuCN was added. The resulting mixture wasstirred for 1 h at −30° C., cooled to −80° C., and a solution of 2.79 g(10.0 mmol) ofchloro(dimethyl)(2-methyl-5-tert-buthyl-1H-inden-7-yl)silane in 15 ml ofether was added dropwise by vigorous stirring for 10 min. This mixturewas stirred for 12 h at room temperature, and then 1 ml of water wasadded. The mixture was stirred for 5 min and passed through short columnwith Silica Gel 60 (40-63 um, d 50 mm, l 30 mm). The silica gel layerwas additionally washed by 100 ml of ether. The combined elute wasevaporated to dryness. The product was isolated from the residue byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, l 50 mm; eluent: hexanes). Yield 3.28 g (88%) ofdimethyl(2-methyl-5-tert-buthyl-1H-inden-7-yl)(3-methyl-1H-inden-1-yl)silane.

Anal. calc. for C₂₆H₃₂Si: C, 83.81; H, 8.66. Found: C, 83.62; H, 8.75.

¹H NMR (CDCl₃): δ 7.39-7.44 (m, 2H, 4,7-H in 3-methylinden-1-yl),7.24-7.33 (m, 2H, 4,5-H in 2-methyl-5-tert-buthylinden-7-yl), 7.12-7.15(m, 2H, 5,6-H in 3-methylinden-1-yl), 6.55 (m, 1H, 3-H in2-methyl-5-tert-buthylinden-7-yl), 6.32 (m, 1H, 2-H in3-methylinden-1-yl), 3.76 (m, 1H, 1-H in 3-methylinden-1-yl), 3.32 (m,2H, 1,1′-H in 2-methyl-5-tert-buthylinden-7-yl), 2.25 (s, 3H, Me in3-methylinden-1-yl), 2.20 (s, 3H, Me in2-methyl-5-tert-buthylinden-7-yl), 1.39 (s, 9H, 5-C(CH₃)₃), 0.27 (s, 3H,SiMeMe′), 0.22 (s, 3H, SiMeMe′).

¹³C{¹H} NMR (CDCl₃): δ 148.4, 146.0, 145.8, 145.5, 145.4, 145.3, 137.4,131.1, 130.6, 127.3, 126.7, 124.7, 123.5, 123.1, 118.8, 118.2, 43.8,43.5, 34.6, 31.6, 16.7, 12.9, −3.3, −4.1.

Complex 21-Zr

To a solution of 3.09 g (10.0 mmol) of(6/5-tert-butyl-2-methyl-1H-inden-4/7-yl)(cyclopenta-2,4-dien-1-yl)dimethylsilanein 200 ml of ether 8.0 ml of 2.5 M (20 mmol) of n-BuLi in hexanes wasadded by vigorous stirring for 5 min at room temperature. This mixturewas stirred for 12 h, then cooled to −30° C., and 3.77 g (10 mmol) ofZrCl₄(THF)₂. The resulting mixture was stirred for 24 h at roomtemperature and then evaporated to dryness. A mixture of the residueobtained and 200 ml of toluene was stirred for 6 h at 80° C. and thenfiltered through glass frit (G4). The precipitate was additionallywashed by 3×50 ml of hot toluene. The combined extract was evaporated todryness, and the residue was re-crystallized from 15 ml of toluene.Crystals precipitated at −30° C. were collected, washed by 3×2 ml ofcold toluene, 2×10 ml of hexanes, and dried in vacuum. Yield 2.25 g(48%).

Anal. calc. for C₂₁H₂₆Cl₂SiZr: C, 53.82; H, 5.59. Found: C, 54.03; H,5.70.

¹H NMR (CD₂Cl₂): δ 7.52 (m, 1H, 7-H in indenyl), 7.21 (m, 1H, 5-H inindenyl), 6.82 (m, 1H, C₅H₄), 6.60 (m, 1H, C₅H₄), 6.49 (m, 1H, 3-H inindenyl), 6.36 (m, 1H, 1-H in indenyl), 6.29 (m, 1H, C₅H₄), 5.37 (m, 1H,C₅H₄), 2.29 (s, 3H, 2-Me in indenyl), 1.34 (s, 9H, 6-C(CH₃)₃ inindenyl), 0.92 (s, 3H, SiMeMe′), 0.64 (s, 3H, SiMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 150.2, 140.6, 134.6, 132.6, 126.7, 126.1, 124.7,120.6, 119.5, 118.3, 117.8, 112.4, 108.8, 98.4, 34.9, 30.8, 16.8, −3.3,−4.5.

Complex 21-Hf

To a solution of 3.09 g (10.0 mmol) of(6/5-tert-butyl-2-methyl-1H-inden-4/7-yl)(cyclopenta-2,4-dien-1-yl)dimethylsilanein 200 ml of ether 8.0 ml of 2.5 M (20 mmol) of n-BuLi in hexanes wasadded by vigorous stirring for 5 min at room temperature. This mixturewas stirred for 12 h, then cooled to −30° C., and 4.64 g (10 mmol) ofHfCl₄(THF)₂. The resulting mixture was stirred for 24 h at roomtemperature and then evaporated to dryness. A mixture of the residueobtained and 200 ml of toluene was stirred for 6 h at 80° C. and thenfiltered through glass frit (G4). The precipitate was additionallywashed by 3×50 ml of hot toluene. The combined extract was evaporated todryness, and the residue was re-crystallized from 15 ml of toluene.Crystals precipitated at −30° C. were collected, washed by 3×2 ml ofcold toluene, 2×10 ml of hexanes, and dried in vacuum. Yield 2.56 g(46%).

Anal. calc. for C₂₁H₂₆Cl₂SiHf: C, 45.37; H, 4.71. Found: C, 45.55; H,4.86.

¹H NMR (CD₂Cl₂): δ 7.49 (m, 1H, 7-H in indenyl), 7.23 (m, 1H, 5-H inindenyl), 6.73 (m, 1H, C₅H₄), 6.52 (m, 1H, C₅H₄), 6.31 (m, 1H, 3-H inindenyl), 6.24 (m, 1H, 1-H in indenyl), 6.22 (m, 1H, C₅H₄), 5.27 (m, 1H,C₅H₄), 2.38 (s, 3H, 2-Me in indenyl), 1.36 (s, 9H, 6-C(CH₃)₃ inindenyl), 0.92 (s, 3H, SiMeMe′), 0.66 (s, 3H, SiMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 149.8, 139.5, 134.0, 133.6, 126.6, 124.4, 122.6,119.4, 119.0, 117.3, 116.4, 111.5, 106.5, 96.3, 34.8, 30.8, 16.7, −3.3,−4.4.

Complex 22-Zr

To a solution of 3.73 g (10.0 mmol) of(6/5-tert-butyl-2-methyl-1H-inden-4/7-yl)(dimethyl)(3-methyl-1H-inden-1-yl)silanein 200 ml of ether 8.0 ml of 2.5 M (20 mmol) of n-BuLi in hexanes wasadded by vigorous stirring for 5 min at room temperature. This mixturewas stirred for 12 h, then cooled to −30° C., and 3.77 g (10 mmol) ofZrCl₄(THF)₂. The resulting mixture was stirred for 24 h at roomtemperature and then evaporated to dryness. A mixture of the residueobtained and 200 ml of toluene was stirred for 6 h at 80° C. and thenfiltered through glass frit (G4). The precipitate was additionallywashed by 3×50 ml of hot toluene. The combined extract was evaporated todryness, and the residue was re-crystallized from 30 ml of toluene.Crystals precipitated at −30° C. were collected, washed by 3×4 ml ofcold toluene, 2×7 ml of hexanes, and dried in vacuum. Yield 2.61 g (49%)of one pure isomer.

Anal. calc. for C₂₆H₃₀Cl₂SiZr: C, 58.62; H, 5.68. Found: C, 58.89; H,5.79.

¹H NMR (CD₂Cl₂): δ 7.35-7.40 (m, 3H, 5,7-H in 2-methylindenyl and 4-H in3-methylindenyl), 7.10 (m, 1H, 5-H in 3-methylinden-1-yl), 6.88 (m, 1H,6-H in 3-methylinden-1-yl), 6.75 (d, J=7.6 Hz, 7-H in 3-methylindenyl)6.48 (m, 1H, 3-H in 2-methylindenyl), 6.45 (m, 1H, 1-H in2-methylindenyl), 6.27 (m, 1H, 2-H in 3-methylindenyl), 2.49 (s, 3H, Mein 3-methylinden-1-yl), 2.24 (s, 3H, Me in 2-methylinden), 1.34 (s, 9H,5-C(CH₃)₃ in 2-methylindenyl), 1.02 (s, 3H, SiMeMe′), 0.89 (s, 3H,SiMeMe′).

¹³C{¹H} NMR (CD₂Cl₂): δ 149.9, 139.7, 133.8, 132.1, 131.3, 129.3, 127.0,126.6, 126.4, 126.1, 125.8, 123.5, 121.0, 119.3, 117.4, 108.7, 99.2,98.9, 34.8, 30.6, 16.8, 13.7, −1.9, −4.0.

Example 8 4-Bromo-6-tertbutyl-1-methoxy-2-methylindane

To a solution of 104 g (0.37 mol) of 4-bromo-6-tert-buthyl-1-indanone in800 ml of THF-methanol (2:1, vol.) 22.5 g (0.592 mol) of NaBH₄ was addedin small portions with vigorous stirring over 1.5 h at 5° C. Thismixture was stirred at room temperature for 12 h and then added to 1500cm³ of cold water. The hydrogenation product was extracted with 3×300 mlof dichloromethane, and the combined extract was evaporated to dryness.To 62 g (1.11 mol) of KOH in 510 ml of DMSO, 131 g (0.92 mol) MeI and asolution of crude 4-bromo-6-tertbuthylindan-1-ol in 150 ml of DMSO wereadded. This mixture was stirred for 4 h at ambient temperature. Theresulting mixture was added to 2 L of cold water. The crude product wasextracted with 4×400 ml of dichloromethane. The combined extract wasdried over Na₂SO₄ and then evaporated to dryness. Fractionaldistillation gave a mixture of two diastereomeric compounds, b.p. 121°C./3 mm Hg. Yield 87.2 g (79%) of colorless oil of pure4-bromo-6-tertbutyl-1-methoxy-2-methylindane of a ca. 1 (trans-isomer)to 2 (cis-isomer) mixture of two diastereomers.

Anal. calc. for C₁₅H₂₁BrO: C, 60.61; H, 7.12. Found: C, 60.60; H, 7.13.

¹H NMR (CDCl₃): δ 7.43 (s, 1H, cis-product), 7.41 (s, 1H,trans-product), 7.31 (s, 1H, cis-product), 7.30 (s, 1H, trans-product),4.57 (d, J=5.31 Hz, 1H, CHOMe of trans-product), 4.43 (d, J=4.30 Hz, 1H,CHOMe of cis-product), 3.45 (s, 3H, OMe of cis-product), 3.42 (m, 3H,OMe of trans-product), 3.18 (dd, J=16.17 Hz, J=7.08 Hz, 1H, CHMecis-product), 2.94-2.87 (m, 1H, CHMe trans-product), 2.67-2.63 (m, 2H,CH₂ of trans-product), 2.54-2.48 (m, 1H, CHHCHMe of cis-product), 2.40(dd, J=16.17 Hz, J=5.31 Hz, 1H, CHHCHMe of cis-product), 1.31 (s, 9H,tBu of both isomers), 1.18 (d, J=7.08 Hz, 3H, CHMe of cis-product), 1.08(d, J=6.82 Hz, 3H, CHMe of trans-product).

2-(6-tert-Butyl-1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethanol

To a solution of 40.0 g (134.5 mmol) of4-bromo-6-tert-butyl-1-methoxy-2-methylindane in 250 ml of THF 107.7 mlof 2.5 M (269 mmol) n-BuLi in hexanes was added for 20 min at −80° C.This mixture was stirred for 40 min at this temperature, cooled to −110°C., and 11.85 g (269.15 mmol) of ethylene oxide was added by one portionat vigorous stirring. The resulting mixture was stirred for 12 h at roomtemperature, and then 10 ml of water was added. The organic layer wasseparated and evaporated to dryness. To the residue 200 ml of water wasadded, and the crude product was extracted with 3×100 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyusing short column with Silica Gel 60 (40-63 um, d 110 mm, l 90 mm;eluent: hexanes/ether=20/1). Yield 27.58 g (78%) of a ca. 1 to 2 mixtureof two diastereomers.

Anal. calc. for C₁₇H₂₆O₂: C, 77.82; H, 9.99. Found: C, 77.84; H, 9.95.

¹H NMR (CDCl₃): δ 7.28 (s, 1H, of both isomers), 7.14 (s, 1H, of bothisomers), 4.50 (d, J=5.30 Hz, 1H, CHOMe of minor isomer), 4.39 (d,J=4.29 Hz, 1H, CHOMe of major isomer), 3.78 (m, CH2, Ch2CH2 both), 3.47(s, 3H, OMe of major isomer), 3.42 (s, 3H, OMe of minor isomer),3.19-3.15 (m, 1H, CHCH₃ of both isomers), 2.82 (m, 2H, CH₂CH₂ of bothisomers), 2.65-2.60 (m, 1H, CH₂CHCH3 of both isomers), 2.37 (m, 1H,CH₂CHCH3 of both isomers), 1.32 (s, 9H, tBu of both isomers), 1.17 (d,J=7.07 Hz, 3H, Me in MeCH of major isomer), 1.10 (d, J=6.56 Hz, 3H, Mein MeCH of minor isomer).

¹³C{¹H} NMR (CDCl₃): δ 150.14, 149.76, 142.80, 142.28, 139.49, 139.12,135.92, 133.92, 126.43, 126.18, 120.40, 120.32, 91.79, 85.48, 62.78,62.71, 56.91, 56.50, 39.60, 38.55, 36.98, 36.88, 36.71, 36.39, 31.61,19.7, 13.80.

4-(2-Bromoethyl)-6-tert-butyl-1-methoxy-2-methylindane

To a mixture of 27.58 g (105 mmol) of2-(6-tert-butyl-1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethanol and27.58 g (105 mmol) PPh₃ in 450 ml of THF 18.72 g (105 mmol) of NBS wasadded at vigorous stirring for 5 min at 0° C. This mixture was stirredfor 2 h at room temperature and then evaporated to dryness. A solutionof the residue in 500 ml of hexanes was filtered through glass frit(G3), and the precipitate was additionally washed by 3×300 ml hexanes.The combined organic extract was evaporated to dryness. The product wasisolated from the residue using flash chromatography on Silica Gel 60(40-63 um, d 80 mm, 1250 mm; eluent: hexanes/ether=20/1, vol.). Yield25.48 g (74%) of ca. 1 to 2 mixture of diastereomers.

Anal. calc. for C₁₇H₂₅BrO: C, 62.77; H, 7.75; Br, 24.56. Found: C,62.74; H, 7.78; Br, 24.53.

¹H NMR (CDCl₃): δ 7.35 (s, 1H, of both isomers), 7.18 (s, 1H, of bothisomers), 4.55 (d, J=5.56 Hz, 1H, CHOMe of minor isomer), 4.44 (d,J=4.04 Hz, 1H, CHOMe of major isomer), 3.55 (t, J=8.08 Hz, 2H, CH₂CH₂both), 3.51 (s, 3H, OMe of major isomer), 3.46 (s, 3H, OMe of minorisomer), 3.21 (m, 1H, CHCH₃ of both isomers), 3.16 (t, J=8.08 Hz, 2H,CH₂CH₂ of both isomers), 2.56 (m, 1H, CH₂CHCH₃ of both isomers), 2.40(m, 1H, CH₂CHCH₃ of both isomers), 1.327 (s, 9H, t-Bu of both isomers),1.22 (d, J=6.82 Hz, 3H, Me in MeCH of major isomer), 1.15 (d, J=6.57 Hz,3H, Me in MeCH of minor isomer).

2-[2-(6-tert-Butyl-1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-ol

8.59 g (34.84 mmol) of anhydrous CeCl₃ was added to 127 ml of THF at 0°C. This mixture was stirred at room temperature overnight. In anotherflask, to 0.85 g (34.84 mmol) of magnesium turnings in 80 ml of THF11.33 g (34.84 mmol) of4-(2-bromoethyl-6-tert-butyl-1-methoxy-2-methylindane was added dropwisefor 30 minutes at reflux. The resulting mixture was refluxed for 2hours, cooled to 0° C., and then added to a suspension of CeCl₃ in THF.The resulting mixture was stirred for 2 h at room temperature, thencooled to 0° C., and 4.60 g (34.83 mmol) of indanone-2 was added. Thismixture was stirred overnight at room temperature, evaporated todryness. To the residue a mixture of AcOH (20 ml) and water (100 ml) wasadded. The crude product was extracted by 3×150 ml of CH₂Cl₂. Thecombined extract was evaporated to dryness. The product was isolated byflash chromatography using a short column with Silica Gel 60 (40-63 um,d 60 mm, 170 mm; eluent: hexanes/ether=3/1). Yield 5.78 g (44%) of pure2-[2-(6-ten-butyl-1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-olas single diastereomer.

Anal. calc. for C₂₆H₃₄O₂: C, 82.49; H, 9.05. Found: C, 82.44; H, 9.07.

¹H NMR (CDCl₃): δ 7.14-7.07 (m, 6H), 4.57 (s, 1H, OH), 4.30 (d, J=3.79Hz, 1H, CHOMe), 3.35 (s, 3H, OMe), 3.03 (m, 1H, CHMe), 2.97-2.84 (m, 4H,2CH₂ in indane), 2.63 (m, 2H, CH₂ in CH₂CH₂), 2.49 (m, 2H, CH₂CHMe),1.81 (m, 2H, CH₂ in CH₂CH₂), 1.24 (s, 9H, tBu), 1.07 (d, J=6.82 Hz, 3H,Me).

6/5-tent-Butyl-4/7-[2-(1H-inden-2-yl)ethyl]-2-methyl-1H-indene

To a hot (110° C.) solution of 5.2 g (13.74 mmol) of2-[2-(6-ten-butyl-1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-olin 110 ml of toluene 0.581 g (3.05 mmol) of TsOH*H₂O was added. Thismixture was refluxed with a Dean-Stark trap for 40 min, and then passedthrough short column with Silica Gel 60 (40-63 um, d 80 mm, l 60 mm).The column was additionally washed with 300 ml of toluene. The combinedelute was evaporated to dryness. The product was isolated by flashchromatography using a short column with Silica Gel 60 (40-63 um, d 60mm, l 70 mm; eluent: hexanes/ether=50/1). Yield 3.52 g (78%) of pure6/5-tert-butyl-4/7-[2-(1H-inden-2-yl)ethyl]-2-methyl-1H-indene.

Anal. calc. for C₂₄H₂₀: C, 91.41; H, 8.59. Found: C, 91.46; H, 8.54.

¹H NMR (CDCl₃): δ 7.45 (m, 1H), 7.35 (m, 1H), 7.30 (d, J=7.07 Hz, 1H),7.26 (s, 1H), 7.18 (d, J=6.32 Hz, 1H), 7.08 (s, 1H), 6.66 (s, 1H), 6.55(s, 1H), 3.42 (s, 2H), 3.30 (s, 2H), 3.03 (m, 2H), 2.91 (m, 2H), 2.22(s, 3H, Me), 1.40 (s, 9H, t-Bu).

¹³C NMR (CDCl₃): δ 150.24, 150.02, 145.91, 145.54, 143.03, 138.57,135.67, 127.68, 126.44, 126.23, 123.63, 123.66, 123.38, 120.80, 119.87,114.97, 41.24, 40.94, 34.62, 33.22, 31.76, 31.67, 16.81.

Complex 23-Hf

To a solution of 2.30 g (7 mmol) of6-tert-butyl-4-[2-(1H-inden-2-yl)ethyl]-2-methyl-1H-indene in 150 ml ofether was added 5.6 ml (14 mmol) of 2.5 M n-BuLi in hexanes at −40° C.This mixture was stirred for 24 h at room temperature, then 3.251 g (7mmol) of HfCl₄(THF)₂ was added at −30° C. The resulting mixture wasstirred for 24 h at room temperature. The solution was concentrated, theresidue was dissolved in 125 ml of toluene and refluxed for 12 h. Thishot mixture was filtered (G4); the filtrate was evaporated to ca. ¼ ofits starting volume. The formed at −30° C. crystals were filtered off(G3) and dried in vacuum. Yield: 1.93 g (48%) yellow crystals ofcomplex.

Anal. calcd for: C₂₅H₂₆Cl₂Hf: C, 52.14; H, 4.55; Cl, 12.31; Hf, 30.99%.Found: C, 52.18; H, 4.51; Cl, 12.34; Hf, 30.96%.

¹H NMR (CD₂Cl₂.): δ 7.57 (m, 1H, unsubstituted indene), 7.38 (s, 1H,t-Bu-indene), 7.24 (s, 1H, t-Bu-indene), 7.09 (m, 3H, unsubstitutedindene), 6.15 (s, 1H, Cp), 5.96 (s, 1H, Cp), 5.94 (s, 1H, Cp), 4.24 (s,1H, Cp), 3.78 (m, 1H, CH₂), 3.63 (m, 1H, CH₂), 3.47 (m, 1H, CH₂), 3.32(m, 1H, CH₂), 2.4 (s, 3H, Me), 1.38 (s, 9H, tBu).

¹³C NMR (CD₂Cl₂): δ 149.53, 140.35, 135.5, 135.12, 129.46, 127.92,126.75, 117.99, 125.39, 125.07, 124.95, 124.63, 123.92, 117.5, 107.8,102.34, 99.14, 96.29, 34.9, 30.74, 29.29, 26.61, 16.97.

Example 9 2,5,6-Trimethylindan-1-one

To a suspension of 557 g (4.2 mol) AlCl₃ in 500 ml of CH₂Cl₂ 362 g (1.58mol) of 2-bromo-2-methylpropanoyl bromide was added dropwise withvigorous stirring over 15 min at 0° C. This mixture was stirred for 45min at this temperature; then, a solution of 167 g (1.58 mol) ofo-xylene in 200 ml of CH₂Cl₂ was added dropwise. The mixture was slowlywarmed to ambient temperature, stirred additionally overnight, and thenpoured onto 2000 cm³ of ice. The organic layer was separated, and theaqueous layer was extracted with 3×500 ml of CH₂Cl₂. The combinedextract was dried over MgSO₄ and evaporated to dryness. Fractionaldistillation gave a yellowish mixture of the title indanones, b.p.143-148° C./7 mm Hg. This mixture was recrystallized from 800 ml ofn-hexane. Crystals of 2,5,6-trimethylindan-1-one precipitated at −30° C.were filtered off, washed with 2×40 ml of cold n-hexane, and dried invacuum. Yield 57.8 g (21%) of 2,5,6-trimethylindan-1-one.

Anal. calc. for C₁₂H₁₄O: C, 82.72; H, 8.10. Found: C, 82.74; H, 8.12.

¹H NMR (CDCl₃): δ 7.49 (s, 1H, 4-H), 7.09 (s, 1H, 7-H), 3.29 (dd, J=16.9Hz, J=7.6 Hz, 1H, CHMe), 2.67-2.59 (m, 2H, CH₂), 2.32 (s, 3H, Me), 2.28(s, 3H, Me), 1.27 (d, J=7.6 Hz, MeCH).

4-Bromo-2,5,6-trimethylindan-1-one

In a three-necked round-bottom 500-ml flask equipped with a refluxcondenser, a dropping funnel with a pressure-equalizing bypass, and amechanical stirrer, to a suspension of 53 g (0.398 mol) of AlCl₃ in 60ml of CH₂Cl₂ a solution of 57.8 g (0.332 mol) of2,5,6-trimethylindanone-1 in 50 ml of CH₂Cl₂ was added dropwise withvigorous stirring over 1 h at −10° C. This mixture was stirred for anadditional 1 h at this temperature; then, 17.0 ml (53.0 g, 0.332 mol) ofbromine was added dropwise with vigorous stirring over 1 h. Theresulting mixture was stirred for 2 h at −10° C. and overnight atambient temperature and then poured into 1000 cm³ of cold water. Theorganic layer was separated, and the aqueous layer was extracted with3×200 ml of methyl-tert-butyl ether. The combined extract was washedwith saturated aqueous Na₂SO₃ to eliminate bromine and then with aqueousNa₂CO₃, dried over K₂CO₃, and evaporated to dryness. Fractionaldistillation gave a yellowish liquid, b.p. 155-158° C./4 mm Hg. Yield61.6 g (73%).

Anal. calc. for C₁₂H₁₃BrO: C, 56.94; H, 5.18. Found: C, 56.91; H, 5.16.

¹H NMR (CDCl₃): δ 7.03 (s, 1H, 7-H), 2.91 (dd, J₁=17.43 Hz, J₂=7.58 Hz,1H, CHMe), 2.24 (d, J=17.43 Hz, 1H, CHH), 2.14 (d, J=17.43 Hz, 1H, CHH),2.09 (s, 3H, Me), 2.06 (s, 3H, Me), 1.04 (d, J=7.58 Hz, 3H, CHMe).

¹³C{¹H} NMR (CDCl₃): δ 207.0, 150.74, 142.81, 137.32, 134.8, 123.8,122.4, 41.44, 36.1, 20.73, 19.3, 15.6.

4-Bromo-1-methoxy-2,5,6-trimethylindane

To a solution of 61.6 g (0.243 mol) of4-bromo-2,5,6-trimethyl-1-indanone in 600 ml of THF-methanol (2:1, vol.)14.71 g (0.389 mol) of NaBH₄ was added in small portions with vigorousstirring over 1.5 h at 5° C. This mixture was stirred at roomtemperature for 12 h and then added to 1500 cm³ of cold water. Thehydrogenation product was extracted with 3×200 ml of dichloromethane,and the combined extract was evaporated to dryness. To 54.43 g (0.972mol) of KOH in 420 ml of DMSO, 68.7 g (30.15 ml, 0.486 mol) MeI and asolution of crude 4-bromo-2,5,6-trimethylindan-1-ol in 100 ml of DMSOwere added. This mixture was stirred for 2 h at ambient temperature;then, 92.0 g (15.07 ml, 0.243 mol) of MeI was added, and the mixture wasadditionally stirred for 2 h. The resulting mixture was added to 1.5 Lof cold water. The crude product was extracted with 4×200 ml ofdichloromethane. The combined extract was dried over Na₂SO₄ and thenevaporated to dryness. Fractional distillation gave a mixture of twodiastereomeric compounds, b.p. 115° C./3 mm Hg. Yield 59.5 g (91%) ofcolorless oil of pure 4-Bromo-1-methoxy-2,5,6-trimethylindane of a ca. 2(trans-isomer) to 3 (cis-isomer) mixture of two diastereomers.

Anal. calc. for C₁₃H₁₇BrO: C, 58.01; H, 6.37. Found: C, 58.00; H, 6.38.

¹H NMR (CDCl₃): δ 7.13 (s, 1H, 7-H of cis-product), 7.11 (s, 1H, 7-H oftrans-product), 4.56 (d, J=5.81 Hz, 1H, CHOMe of trans-product), 4.43(d, J=3.79 Hz, 1H, CHOMe of cis-product), 3.45 (m, 3H, OMe ofcis-product), 3.41 (m, 3H, OMe of trans-product), 3.27-3.42 (m, 1H, CHMeof cis-product), 2.99-2.93 (m, 1H, CHMe of trans-product), 2.73-2.58 (m,1H, CHHCHMe of both isomers), 2.54-2.42 (m, 1H, CHHCHMe of bothisomers), 2.37 (s, 3H, Me in both isomers), 2.34 (s, 3H, Me in bothisomers), 1.18 (d, J=7.07 Hz, 3H, CHMe of cis-product), 1.12 (d, J=6.83Hz, 3H, CHMe of trans-product).

¹³C{¹H} NMR (CDCl₃), major isomer: δ 141.6, 140.5, 136.6, 136.05,125.48, 123.5, 92.25, 56.4, 40.85, 39.0, 21.45, 19.58, 13.65.

2-(1-Methoxy-2,5,6-trimethyl-2,3-dihydro-1H-inden-4-yl)ethanol

To a solution of 52.77 g (196.0 mmol) of4-bromo-1-methoxy-2,5,6-trimethylindane in 300 ml of THF 156.8 ml of 2.5M (392.1 mmol) n-BuLi in hexanes was added for 20 min at −80° C. Thismixture was stirred for 40 min at this temperature, cooled to −110° C.,and 17.27 g (392.1 mmol) of ethylene oxide was added by one portion atvigorous stirring. The resulting mixture was stirred for 12 h at roomtemperature, and then 10 ml of water was added. The organic layer wasseparated and evaporated to dryness. To the residue 200 ml of water wasadded, and the crude product was extracted with 3×100 ml ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The product was isolated by flash chromatographyusing short column with Silica Gel 60 (40-63 um, d 110 mm, l 90 mm;eluent: hexanes/ether=20/1). Yield 36.66 g (80%) of a ca. 1 to 1.7mixture of two diastereomers.

Anal. calc. for C₁₅H₂₂O₂: C, 76.88; H, 9.46. Found: C, 76.86; H, 9.45.

¹H NMR (CDCl₃): δ 7.09 (s, 1H, of minor isomer), 7.07 (s, 1H, of majorisomer), 4.46 (d, J=5.581 Hz, 1H, CHOMe of minor isomer), 4.34 (d,J=3.53 Hz, 1H, CHOMe of major isomer), 3.71 (dt, J₁=7.32 Hz, J₂=2.53 Hz,2H, CH₂OH of both isomers), 3.43 (s, 3H, OMe of major isomer), 3.39 (s,3H, OMe of minor isomer), 3.21 (m, 1H, CHCH₃ of both isomers), 2.91 (dt,J₁=7.33 Hz, J₂=2.53 Hz, 2H, CH₂CH₂OH of both isomers), 2.67-2.37 (m, 2H,CH₂CHCH₃ of both isomers), 2.27 (s, 3H, Me of both isomers), 2.22 (s,3H, Me of both isomers), 1.13 (d, J=7.07 Hz, 3H, Me in MeCH of majorisomer), 1.10 (d, J=6.83 Hz, 3H, Me in MeCH of minor isomer).

¹³C{¹H} NMR (CDCl₃), major isomer: δ 140.53, 139.17, 135.54, 135.06,132.44, 125.17, 91.75, 62.02, 56.39, 39.24, 37.70, 33.86, 21.06, 19.7,13.80.

4-(2-Bromoethyl)-1-methoxy-2,5,6-trimethylindane

To a mixture of 36.66 g (156.44 mmol) of2-(1-methoxy-2,5,6-trimethyl-2,3-dihydro-1H-inden-4-yl)ethanol and 41 g(156.44 mmol) PPh₃ in 650 ml of THF 27.85 g (156.44 mmol) of NBS wasadded at vigorous stirring for 5 min at 0° C. This mixture was stirredfor 2 h at room temperature and then evaporated to dryness. A solutionof the residue in 500 ml of hexanes was filtered through glass frit(G3), and the precipitate was additionally washed by 3×300 ml hexanes.The combined organic extract was evaporated to dryness. The product wasisolated from the residue using flash chromatography on Silica Gel 60(40-63 um, d 80 mm, 1250 mm; eluent: hexanes/ether=20/1, vol.). Yield31.38 g (67%) of ca. 1 to 2 mixture of diastereomers.

Anal. calc. for C₁₅H₂₁BrO: C, 60.61; H, 7.12. Found: C, 60.64; H, 7.16.

¹H NMR (CDCl₃): δ 7.14 (s, 1H, of major isomer), 7.13 (s, 1H, of minorisomer), 4.49 (d, J=5.55 Hz, 1H, CHOMe of minor isomer), 4.37 (d, J=3.53Hz, 1H, CHOMe of major isomer), 3.46 (s, 3H, OMe of major isomer), 3.42(s, 3H, OMe of minor isomer), 3.43-3.38 (m, 2H, CH₂Br of both isomers),3.25-3.17 (m, 2H, CH₂CH₂Br of both isomers), 2.95 (m, 1H, CH₂CHCH₃ ofboth isomers), 2.70-2.50 (m, 2H, CHHCHCH₃ of both isomers), 2.30 (s, 3H,Me of both isomers), 2.24 (s, 3H, Me of both isomers), 1.17 (d, J=7.05Hz, 3H, MeCH of major isomer), 1.14 (d, J=6.82 Hz, 3H, MeCH of minorisomer).

2-[2-(1-Methoxy-2,5,6-trimethyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-ol

13.6 g (54.9 mmol) of anhydrous CeCl₃ was added to 200 ml of THF at 0°C. This mixture was stirred at room temperature overnight. In anotherflask, to 1.34 g (54.9 mmol) of magnesium turnings in 125 ml of THF16.33 g (54.94 mmol) of 4-(2-bromoethyl-1-methoxy-2,5,6-trimethylindanewas added dropwise for 30 minutes at reflux. The resulting mixture wasrefluxed for 2 hours, cooled to 0° C., and then added to a suspension ofCeCl₃ in THF. The resulting mixture was stirred for 2 h at roomtemperature, then cooled to 0° C., and 7.26 g (54.94 mmol) of indanone-2was added. This mixture was stirred overnight at room temperature,evaporated to dryness. To the residue a mixture of AcOH (30 ml) andwater (170 ml) was added. The crude product was extracted by 3×200 ml ofCH₂Cl₂. The combined extract was evaporated to dryness. The product wasisolated by flash chromatography using a short column with Silica Gel 60(40-63 um, d 60 mm, l 70 mm; eluent: hexanes/ether=3/1). Yield 6.60 g(40%) of pure2-[2-(1-methoxy-2,5,6-trimethyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-olof a ca. 1 to 3.5 mixture of two diastereomers.

Anal. calc. for C₂₄H₃₀O₂: C, 82.24; H, 8.63. Found: C, 82.26; H, 8.61.

¹H NMR (CDCl₃): δ 7.19 (m, 2H, aromatics in both isomers), 7.12 (m, 2H,aromatics in both isomers), 6.98 (s, 1H, H in 2,5,6-trimethylindane inboth isomers), 4.64 (s, 1H, OH of both isomers), 4.39 (d, J=4.80 Hz, 1H,CHOMe of minor isomer), 4.27 (d, J=2.78 Hz, 1H, CHOMe of major isomer),3.31 (s, 3H, OMe of major isomer), 3.26 (s, 3H, OMe of minor isomer),3.09 (m, 4H, 2CH₂ in indanole fragment of minor isomer), 2.99 (d,J=16.17 Hz, 2H, CH₂ in indanole fragment of major isomer), 2.92 (d,J=16.17 Hz, 2H, CH₂ in indanole fragment of major isomer), 2.70 (m, 2H,CH₂CH₂CHOH in both isomers), 2.50 (m, 1H, CH₂CHMe in both isomers), 2.35(m, 2H, CH₂CHMe in both isomers), 2.21 (s, 3H, CH₃ in both isomers),2.16 (s, 3H, CH₃ in both isomers), 1.70 (m, 2H, CH₂CH₂CHOH in bothisomers), 1.06 (d, J=6.57 Hz, 3H, MeCH major isomer), 1.01 (d, J=6.57Hz, 3H, MeCH minor isomer).

4/7-[2-(1H-Inden-2-yl)ethyl]-2,5,6-trimethyl-1H-indene

To a hot (110° C.) solution of 6.0 g (18.61 mmol) of2-[2-(1-methoxy-2,5,6-trimethyl-2,3-dihydro-1H-inden-4-yl)ethyl]indan-2-olin 130 ml of toluene 0.708 g (3.72 mmol) of TsOH*H₂O was added. Thismixture was refluxed with a Dean-Stark trap for 30 min, and then passedthrough short column with Silica Gel 60 (40-63 um, d 80 mm, l 60 mm).The column was additionally washed with 300 ml of toluene. The combinedelute was evaporated to dryness. The product was isolated by flashchromatography using a short column with Silica Gel 60 (40-63 um, d 60mm, l 70 mm; eluent: hexanes/ether=50/1). Yield 4.58 g (82%).

Anal. calc. for C₂₃H₂₄: C, 91.95; H, 8.05. Found: C, 91.93; H, 8.07.

¹H NMR (CDCl₃): δ 7.44 (d, J=7.07 Hz, 1H, 4-H in unsubst. indene), 7.35(d, J=7.33 Hz, 1H, 7-H in unsubst. indene), 7.28 (t, J=7.33 Hz, 1H, 6-Hin unsubst. indene), 7.17 (t, J=7.07 Hz, 1H, 5-H in unsubst. indene),7.02 (s, 1H, H in 2,5,6-trimethylindene), 6.67 (s, 1H, vinyl), 6.46 (s,1H, vinyl), 3.43 (s, 2H, CH₂ in indene), 3.27 (s, 2H, CH₂ in indene),3.03 (m, 2H, CH₂ in CH₂CH₂), 2.71 (m, 2H, CH₂ in CH₂CH₂), 2.35 (s, 3H,Me), 2.30 (s, 3H, Me), 2.17 (s, 3H, Me).

¹³C{¹H} NMR (CDCl₃): δ 150.39, 145.52, 144.62, 143.18, 143.01, 139.69,135.10, 134.84, 129.38, 127.26, 126.29, 126.22, 123.73, 123.42, 120.00,119.58, 41.62, 41.16; CH₂ 31.12, 30.69, 21.08, 16.75, 14.81.

Complex 24-Hf

To a solution of 2.14 g (7.12 mmol) of4/7-[2-(1H-inden-2-yl)ethyl]-2,5,6-trimethyl-1H-indene in 150 ml ofether was added 5.7 ml (14.24 mmol) of 2.5 M n-BuLi in hexanes at −40°C. This mixture was stirred for 24 h at room temperature, then 3.307 g(7.12 mmol) of HfCl₄(THF)₂ was added at −30° C. The resulting mixturewas stirred for 24 h at room temperature. The solution was concentrated,the residue was dissolved in 125 ml of toluene and refluxed for 12 h.This hot mixture was filtered (G4); the filtrate was evaporated to ca.1/4 of its starting volume. The formed at −30° C. crystals were filteredoff (G3) and dried in vacuum. Yield: 1.68 g (43%) yellow crystals ofcomplex.

Anal. Calcd for: C₂₃H₂₂Cl₂Hf: C, 50.43; H, 4.05; Cl, 12.94; Hf, 32.58%.Found: C, 50.45; H, 4.07; Cl, 12.91; Hf, 32.56%.

¹H NMR (CD₂Cl₂.): δ 7.54-7.52 (m, 1H, unsubstituted indene), 7.25 (s,1H, trimethylindene), 7.15 (m, 1H, unsubstituted indene), 7.10-7.08 (m,2H, unsubstituted indene), 6.06 (d, J=2.52 Hz, 1H, vinyl intrimethylindene), 6.03 (d, J=3.28 Hz, 2H, vinyl in unsubstitutedindene), 4.41 (d, J=2.52 Hz, 1H, vinyl in trimethylindene), 3.64-3.55(m, 2H, CH₂), 3.52-3.41 (m, 1H, CHH), 3.34-3.27 (m, 1H, CHH), 2.41 (s,6H, 5-Me and 6-Me), 2.34 (s, 3H, 2-Me).

¹³C{¹H} NMR (CD₂Cl₂): δ 139.15, 136.95, 135.16, 132.27, 131.19, 128.96,128.65, 128.15, 127.64, 125.28, 124.97, 124.90, 124.83, 121.58, 106.63,101.73, 99.13, 96.83, 27.45, 25.05, 21.56, 16.96, 14.94.

Example 10 4/7-(2-bromoethyl)-2,5,6-trimethyl-1H-indene

To a hot (110° C.) solution of 6.28 g (21.13 mmol) of4-(2-bromoethyl)-1-methoxy-2,5,6-trimethylindane in 75 ml of toluene 0.4g of TsOH*H₂O was added. This mixture was refluxed with Dean-Stark trapfor 10 min and then passed through the layer of Silica Gel 60 (40-63 um,d 80 mm, l 50 mm). The Silica Gel layer was additionally washed by 300ml of toluene. The combined organic extract was evaporated to dryness.The product was isolated by flash chromatography using a short columnwith Silica Gel 60 (40-63 um, d 80 mm, l 50 mm; eluent: hexanes). Yield5.38 g (96%) of 4-(2-bromoethyl)-2,5,6-trimethyl-1H-indene.

Anal. calc. for C₁₄H₁₇Br: C, 63.41; H, 6.46. Found: C, 63.44; H, 6.48.

¹H NMR (CDCl₃): δ 7.01 (s, 1H, 7-H in indenyl), 6.42 (s, 1H, vinyl),3.47 (t, J=8.84 Hz, 2H, CH₂Br), 3.28 (t, J=8.84 Hz, 2H, CH₂CH₂Br), 3.26(s, 2H, CH₂ in indenyl), 2.31 (s, 3H, Me), 2.24 (s, 3H, Me)), 2.16 (s,3H, Me)

¹³C{¹H} NMR (CDCl₃): δ 144.87, 143.45, 140.33, 135.42, 131.86, 129.63;CH 127.15, 120.45, 41.76, 35.08, 30.48, 21.03, 16.73, 14.94.

4/7-(2-Cyclopenta-2,4-dien-1-ylethyl)-2,5,6-trimethyl-1H-indene

To a solution of 2.68 g (37.11 mmol) of CpLi in 170 ml of TΓΦ a solutionof 9.84 g (37.11 mmol) of 4/7-(2-bromoethyl)-2,5,6-trimethyl-1H-indenein 10 ml of THF was added dropwise by vigorous stirring for 10 min at−80° C. This mixture was stirred for 60 h at room temperature, and then1 ml of water was added. The resulting mixture was evaporated todryness, and 100 ml of water was added to the residue. The crude productwas extracted by 3×50 ml of dichloromethane. The combined organicextract was dried over Na₂SO₄ and evaporated to dryness. The product wasisolated by flash chromatography using a short column with Silica Gel 60(40-63 um, d 80 mm, l 60 mm; eluent: hexanes. Yield 6.87 g (74%) of amixture of isomeric compounds.

Anal. calc. for C₁₉H₂₂: C, 91.14; H, 8.86. Found: C, 91.17; H, 8.83.

¹H NMR (CDCl₃): δ 7.04 (m, 1H), 6.59 (m, 1H), 6.53 (m, 1H), 6.45 (m,1H), 6.33 (m, 1H), 6.15 (m, 1H), 3.50 (m, 2H), 3.29 (s, 2H, CH₂), 3.24(m, 1H), 3.04-2.95 (m, 2H), 3.12 (s, 3H, Me), 2.27 (s, 3H, Me), 2.19 (s,3H, Me).

Complex 25-Zr

To a solution of 2.50 g (10 mmol) of4/7-(2-cyclopenta-1,4-dien-1-ylethyl)-2,5,6-trimethyl-1H-indene in 150ml of ether was added 8 ml (20 mmol) of 2.5 M n-BuLi in hexanes at −40°C. This mixture was stirred for 24 h at room temperature, then 3.77 g(10 mmol) of ZrCl₄(THF)₂ was added at −30° C. The resulting mixture wasstirred for 24 h at room temperature. The solution was concentrated, theresidue was dissolved in 125 ml of toluene and refluxed for 12 h andthen filtered through glass frit (G4). The precipitate was additionallywashed by 3×50 ml of hot toluene. The combined extract was evaporated todryness, and the residue was re-crystallized from 30 ml of toluene.Crystals precipitated at −30° C. were collected, washed by 3×3 ml ofcold toluene, 2×10 ml of hexanes, and dried in vacuum. Yield 1.03 g(25%).

Anal. calc. for C₁₉H₂₀Cl₂Zr: C, 55.59; H, 4.91. Found: C, 55.55; H,4.94.

¹H NMR (CD₂Cl₂): δ 7.33 (s, 1H, 7-H in indenyl), 6.50 (m, 1H, 1-H inindenyl), 6.36 (m, 1H, 3-H in indenyl), 6.26 (m, 1H, CH in Cp), 6.21 (m,1H, CH in Cp), 6.12 (m, 1H, CH in Cp), 4.90 (m, 1H, CH in Cp), 3.43 (m,1H, CH₂CHH), 3.35 (m, 2H, CH₂CH₂), 2.79 (m, 1H, CH₂CHH), 2.35 (s, 3H,Me), 2.30 (s, 3H, Me), 2.25 (s, 3H, Me).

Polymerisation Reactions:

1. Homogeneous Homopolymerisation to Produce HDPE

Complexes were tested in the solution phase ethylene homopolymerisation.

Polymerisations were carried out in a 0.1 L stainless steel autoclavereactor equipped with a paddle stirrer and a continuous supply ofethylene. Ethylene (>99.95%), nitrogen (>99.999%) and pentane, arefurther treated with sets of purifiers removing selectively O₂, H₂O, CO,CO₂ and acetylene.

The complex was pre-contacted with MAO for 1 hour with the aluminium tometal ratio 3000 mol/mol. Toluene was used as solvent.

The reactors were made inert with evacuation and nitrogen flushing. Theactivated complex solution was added to the reactor in an inert nitrogenatmosphere. The polymerisation medium (70 mL Pentane) was added at roomtemperature. The reactor was heated up to 80° C. and the polymerisationstarted by introducing the ethylene. Polymerization was continued for 30minutes at 80° C. and 10 bar ethylene partial pressure. Duringpolymerization, the temperature of the reactor, stirring rate, andreactor pressure were maintained constant. The polymerization wasstopped by cutting off the ethylene flow, flushing the reactor withnitrogen and cooling down the reactor to room temperature. The resultantpolymer product was separated from the polymerization medium and driedin fume hood over night.

Polymerization results are presented in Table 1.

2. Catalyst Synthesis Method A:

Complexes were supported on Grace XPO-2485A 20 um silica, PV=1.4 mL/gSiO2 with the following procedure.

2.6 mL of MAO (30 w-%) was mixed with 0.06 mmol of complex (Al/M ratio200) and 0.18 mL of extra toluene was added on top and stirred 30 min at+25° C. The solution was added to 2.0 g of XPO-2485A during 10-15 minand kept 1 h at +25° C. with occasional stirring. The solvent wasevaporated off under Ar or N2 flow at +25° C. to give powder.

3. Heterogeneous Homopolymerisation to Produce HDPE

Complexes were supported on Grace XPO-2485A 20 um silica, PV=1.4 mL/gSiO2 with the following procedure.

2.6 mL of MAO (30 w-%) was mixed with 0.06 mmol of complex (Al/M ratio200) and 0.18 mL of extra toluene was added on top and stirred 30 min at+25° C. The solution was added to 2.0 g of XPO-2485A during 10-15 minand kept 1 h at +25° C. with occasional stirring. The solvent wasevaporated off under Ar or N2 flow at +25° C. to give powder.

Polymerisations were carried out in a 0.1 L stainless steel autoclavereactor equipped with a paddle stirrer and a continuous supply ofethylene. Ethylene (>99.95%), nitrogen (>99.999%) and isobutane (>97%),are further treated with sets of purifiers removing selectively O₂, H₂O,CO, CO₂ and acetylene.

Prior to the polymerisation the catalyst was weighted to a catalystfeeding vessel in an inert nitrogen atmosphere.

The reactors were made inert with evacuation and nitrogen flushing. Ascavanger was dissolved in a part of the polymerisation medium andprecontacted for 5 minutes with the reactor vessel prior topolymerisation. 0.5 mmol of TiBA per 1 mL of polymerisation medium wasused. The rest of the polymerisation medium was used to feed thecatalyst. In total 70 ml of isobutene or propane was used as thepolymerisation medium. The reactor was heated up to 80° C. and thepolymerisation started by introducing the ethylene. The reactor pressurewas adjusted to the targeted value using the ethylene partial pressureof 5-10 bars. Polymerization was continued for one hour at 80° C. Duringpolymerization, the temperature of the reactor, stirring rate, andreactor pressure were maintained constant.

The polymerization was stopped by cutting off the ethylene flow anddegassing the reactor. After the pressure was completely released andmedium evaporated the reactor was opened. Resultant polymer product wasdried in fume hood over night.

Polymerization results are presented in Table 2.

4. Heterogeneous Copolymerisation to Produce LLDPE

Further heterogeneous polymerisations were carried out in the presenceof the comonomer hexene (1.6 ml) to form an LLDPE. The activity ofcatalysts during polymerisation was measured and are reported in Table3.

For comparative purposes, the metallocenes nBuCp₂ZrCl₂ or nBuCp₂HBz₂were tested under the same conditions for each polymerisation protocol.

As can be seen, the Mw of the polymer formed by the catalysts of theinvention is much higher than those formed under identical conditions bythe prior art metallocenes. The 1-hexene content measured by FT-IR ishigher for many complexes of the invention. Also activity for many ofthe complexes of the invention is comparable to that of the prior artcatalysts.

TABLE 1 RESULTS: HOMOGENEOUS HOMO-POLYMERISATION isomeric ratio[meso-like/ activity Mw complex rac-like] [kgpol/gMe * h] [g/mol] Mw/Mn(n-BuCp)ZrCl₂ 4829 282000 2.2 16-Zr 2:1 1863 836000 2.0 8-Zr 8:1 1076750000 2.1 1-Zr single 86 260000 2.3 17-Zr single 763 835000 4.1 15-Zr3:2 1048 831000 2.4 13-Zr single 316 804000 2.3 9-Zr 7:1 657 992000 2.07-Zr single 305 477000 2.2 10-Zr 6:1 805 965000 1.9 11-Zr single 475618000 2.3 4-Zr 1:1 424 535000 2.3 5-Zr 4:1 356 485000 2.0

TABLE 2 RESULTS: HETEROGENEOUS HOMO-POLYMERISATION isomeric ratioactivity [meso-like/ [kgpol/ Mw Mw/ complex rac-like] medium (gcat * h)][g/mol] Mn (n-BuCp)ZrCl₂ propane 1.16 166000 2.4 (n-BuCp)HfBz₂ propane1.74 108000 2.2 16-Zr 2:1 iso-butane 0.22 743000 2.8 8-Zr 8:1 iso-butane0.21 568000 2.7 1-Zr single iso-butane 0.17 223000 3.4 17-Zr singleiso-butane 0.07 647000 3.4 15-Zr 3:2 iso-butane 0.26 985000 4.0 13-Zrsingle iso-butane 0.18 1054000 3.4 9-Zr 7:1 iso-butane 0.35 862000 3.87-Zr single iso-butane 0.24 545000 3.3 10-Zr 6:1 iso-butane 0.31 9910004.8 11-Zr single iso-butane 0.18 730000 3.2 4-Zr 1:1 iso-butane 0.24434000 3.2 5-Zr 4:1 iso-butane 0.26 528000 2.7 18-Zr single Propane 0.76166000 3.7 14-Zr single Propane 0.38 598000 2.6 14-Hf single Propane0.08 961000 2.8 3-Zr single Propane 0.10 844000 3.2 3-Hf single Propane0.02 748000 4.1 7-Hf single Propane 0.03 765000 3.2 9-Hf single Propane0.02 498000 3.3 19-Zr single Propane 0.40 251000 2.9 19-Hf singlePropane 0.48 609000 2.6 20-Zr 4:1 Propane 0.82 126000 2.9 20-Hf 2:1Propane 0.06 272000 2.8 12-Zr 3:1 Propane 0.30 1193000 2.4 12-Hf singlePropane 0.02 1189000 2.7 11-Hf single Propane 0.03 533000 4.9 10-Hfsingle Propane 0.04 586000 2.7 18-Hf single Propane 0.05 417000 3.8

TABLE 3 RESULTS: HETEROGENEOUS CO-POLYMERISATION ethylene isomeric ratiopartial pressure TiBA activity Mw hexene content complex[meso-like/rac-like] medium [bar] [mmol/L] [kgpol/(gcat * h)] [g{mol]Mw/Mn [%] (n-BuCp)ZrCl₂ propane 10 0.5 0.7 518000 2.6 3.5 (n-BuCp)HfBz₂propane 10 0.5 0.8 290000 2.5 2.8 16-Zr 2:1 iso-butane 5 no 0.30 4840002.6 5.3 8-Zr 8:1 iso-butane 5 no 0.15 461000 4.4 1.1 1-Zr singleiso-butane 5 no 0.13 254000 4.3 4.8 15-Zr * 3:2 iso-butane 5 0.5 0.33405000 5.1 4.5 13-Zr single iso-butane 5 no 0.10 746000 2.2 6.4 9-Zr 7:1iso-butane 5 no 0.16 483000 2.9 7.6 10-Zr * 6:1 iso-butane 5 0.5 0.32544000 2.1 8.0 18-Zr single propane 10 0.5 1.05 140000 3.1 3.9 14-Zrsingle propane 10 0.5 0.92 415000 2.4 3.9 14-Hf single propane 10 0.50.05 676000 3.1 6.6 3-Zr single propane 10 0.5 0.23 655000 2.4 7.3 3-Hfsingle propane 10 0.5 0.01 373000 4.4 10.6 7-Hf single propane 10 0.50.04 395000 4.2 10.6 9-Hf single propane 10 0.5 0.02 254000 3.8 15.919-Zr single propane 10 0.5 0.62 271000 2.4 2.2 19-Hf single propane 100.5 0.50 521000 2.4 3.2 20-Zr 4:1 propane 10 0.5 0.90 146000 2.7 4.820-Hf 2:1 propane 10 0.5 0.07 279000 2.5 6.5 12-Zr 3:1 propane 10 0.50.27 928000 2.4 1.1 12-Hf single propane 10 0.5 0.03 797000 3.2 2.111-Hf single propane 10 0.5 0.02 294000 6.7 9.0 10-Hf single propane 100.5 0.04 298000 2.7 19.3 18-Hf single propane 10 0.5 0.06 283000 2.9 6.65. Catalyst Synthesis Method B:

Complexdimethylsilyl-(2-methyl-6-tert-butyl-inden-4-yl)-cyclopentadienylzirconium dichloride was supported on Grace XPO-2485A 20 μm silica,PV=1.4 mL/g SiO² by the following procedure:

-   1. First, 0.061 mmol of complex was dissolved in a solution    containing 1.3 mL of MAO (30 w-%) and 2.9 mL of toluene to form a    mixture with Al/M ratio 100. The resulting mixture was stirred for    30 min at +25° C. with vortex mixing of 500 rpm.-   2. This solution was added during 10-15 min into 1.0 g of silica    (XPO-2485A). During addition, vortex mixing was 800 rpm. Then, the    system was kept at 3 h at +25° C. with vortex mixing of 500 rpm.-   3. Finally, the solvent was evaporated off under N2 flow at +50° C.    to give catalyst powder. Drying phase lasted 3 h at 300 rpm vortex    mixing.    6. Catalyst Synthesis Method C:

Complexdimethylsilyl-(2-methyl-6-tert-butyl-inden-4-yl)-cyclopentadienylzirconium dichloride was supported on Grace XPO-2485A 20 μm silica,PV=1.4 mL/g SiO2 with the following procedure.

-   1. 1.3 mL of MAO (30 w-%) was contacted with 2.35 mL of toluene for    30 min and then added dropwise on silica. Efficient mixing was    achieved by vortex mixing with 800 rpm.-   2. The resultant reaction mixture was heated up to 80° C. and    reaction was continued for 90 min.-   3. Reaction mixture was cooled down to room temperature and 0.061    mmol complex    (dimethylsilyl-(2-methyl-6-tert-butyl-inden-4-yl)-cyclopentadienyl    zirconium dichloride) dissolved in 0.6 mL of toluene was added onto    MAO treated silica to give a catalyst of Al/Zr ratio 100. After    addition of complex, the resultant solution was kept for 60 min at    room temperature with 500 rpm vortex mixing.-   4. Finally, formed catalyst was dried under N2 flow at +50° C.    Drying phase lasted 3 h at 300 rpm vortex mixing.    7. Heterogeneous Polymerisation Conditions

Polymerisations were carried out in a Büchi 2 L stainless steelautoclave reactor equipped with a paddle stirrer and a continuous supplyof ethylene. Ethylene (>99.95%), nitrogen (>99.999%) and isobutane(>97%), 1-hexene (>99%) are further treated with sets of purifiersremoving selectively O₂, H₂O, CO, CO₂ and acetylene.

First, the reactor was inertized with evacuation and nitrogen flushing.Next, the polymerization medium (1.2 L isobutane) was added to thereactor. Catalyst was weighed and catalyst feeder was closed tightly ina glove box. An appropriate amount of the catalyst (approximately 100mg) prepared was charged to a feeding vessel in glove box and thecatalyst injected to the stirred reactor under N2 pressure. The reactorwas then heated to +80° C. after which the polymerisation was started byadding 25 mL of 1-hexene with continuous feed of ethylene. The reactorpressure was adjusted to the targeted value using the ethylene partialpressure 8 bars. Polymerization was continued for one hour at 80° C.During polymerization, the temperature of the reactor, stirring rate,and reactor pressure were maintained constant. The ethylene consumptionand the reactor temperature were recorded.

The polymerization was stopped by cutting off the ethylene flow anddegassing the reactor. After the pressure was completely released andmedium evaporated (approx 30 minutes) the reactor was opened. Resultantpolymer product was dried in fume hood over night.

Polymerization results are presented in Table 4.

For comparative purposes, a reference catalyst containing metallocenescomplex (n-BuCp)₂HfBz₂ was synthesized and tested under the sameconditions. In reference catalyst synthesis, only complex amount waschanged to (0.077 mmol) give Al:M ratio of 150. In polymerization, about200 mg of catalyst was used in reference polymerization.

As can be seen from Table 4, the Mw of the polymer formed by thiscatalyst of the invention is much higher and comonomer content equalcompared to that formed under identical conditions by the prior artmetallocenes. Catalyst activity is further increased with catalystsynthesis method C. Table 4 also shows measured Al/M ratio based oninductive coupling plasma (ICP) measurement.

ICP analysis: The elemental analysis of a catalyst was performed bytaking a solid sample of mass, M, cooling over dry ice. Samples werediluted up to a known volume, V, by dissolving in nitric acid (HNO₃,65%, 5% of V) and freshly deionised (DI) water (5% of V). The solutionwas then added to hydrofluoric acid (HF, 40%, 3% of V), diluted with DIwater up to the final volume, V, and left to stabilise for two hours.

The analysis was run at room temperature using a Thermo Elemental IRISAdvantage XUV Inductively Coupled Plasma—Atomic Excitation Spectrometer(ICP-AES) which was calibrated immediately before analysis using a blank(a solution of 5% HNO₃, 3% HF in DI water), a low standard (10 ppm Al ina solution of 5% HNO₃, 3% HF in DI water), a high standard (50 ppm Al,50 ppm Hf, 20 ppm Zr in a solution of 5% HNO₃, 3% HF in DI water) and aquality control sample (20 ppm Al, 20 ppm Hf, 10 ppm Zr in a solution of5% HNO₃, 3% HF in DI water).

The content of hafnium was monitored using the 282.022 nm and 339.980 nmlines and the content for zirconium using 339.198 nm line. The contentof aluminium was monitored via the 167.081 nm line, when Alconcentration in ICP sample was between 0-10 ppm and via the 396.152 nmline for Al concentrations between 10-100 ppm.

The reported values, required to be between 0 and 100, or furtherdilution is required, are an average of three successive aliquots takenfrom the same sample and are related back to the original catalyst usingequation 1.

$\begin{matrix}{C = \frac{R \times V}{M}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

Where:

-   -   C is the concentration in ppm, related to % content by a factor        of 10,000    -   R is the reported value from the ICP-AES    -   V is the total volume of dilution in ml    -   M is the original mass of sample in g

If dilution was required then this also needs to be taken into accountby multiplication of C by the dilution factor.

TABLE 4 Catalyst Polymerization Activity prepararation Al:M Yield (kgPE/BD MFR21 Mw Mn 1-Hexene COMPLEX (B or C) (mol:mol) (g) gcat · h) (kg/m³)(g/10 min) (g/mol) (g/mol) Mw/Mn (wt-%) SiMe₂(2-Me-6-t-Bu- B 100 38.60.38 — 0.06 447 000 136 300 3.3 2.8 Ind)CpZrCl₂ C 110 91.8 0.92 395 0.03536 000 172 400 3.1 2.7 REF (n-BuCp)₂HfBz₂ B 150 251.1 1.25 444 2.12 213000 94 900 2.2 2.7 C 160 155.7 1.42 430 2.57 217 000 89 500 2.4 2.9

The invention claimed is:
 1. A complex comprising a ligand of formula(I):

wherein each R¹, which may be the same or different, is hydrogen, anoptionally substituted C₁₋₂₀ hydrocarbyl group, N(R⁵)₂, silyl, siloxy;an optionally substituted heteroaryl group, an optionally substitutedheterocyclyl group or two R¹ groups on adjacent carbon atoms takentogether to form an optionally substituted 5- to 8-membered fused ring;each R², which may be the same or different is hydrogen, is hydrogen, anoptionally substituted C₁₋₂₀ hydrocarbyl group, N(R⁵)₂, silyl, siloxy;an optionally substituted heteroaryl group, or an optionally substitutedheterocyclyl group; R³, which binds the 5-membered ring of the topligand and to the 6-membered ring of the indenyl group, is—(Si(R⁵)₂)_(p)—, where p is 1 or 2, —(C(R₅)₂)_(n)— where n is an integerof 2 or more; each R⁴ which are the same or different, is hydrogen, anoptionally substituted C₁₋₂₀ hydrocarbyl group, N(R⁵)₂, silyl, siloxy,an optionally substituted heteroaryl group, an optionally substitutedheterocyclyl group or two R⁴ groups on adjacent carbon atoms takentogether form an optionally substituted 5- to 8-membered fused carbonring; each R⁵, which are the same or different, is hydrogen, anoptionally substituted C₁₋₂₀ hydrocarbyl group, or two R⁵ groups takentogether form an optionally substituted 5- to 8-membered ring; a is 0 to3; b is 0 to 3 c is 0 to 4; complexed to a metal ion, M.
 2. A complex asclaimed in claim 1 wherein M is a group 4 to 6 metal ion.
 3. A complexas claimed in claim 1 wherein M is Zr or Hf.
 4. A complex as claimed inclaim 1 comprising a ligand of formula (V)

wherein R⁴ and c are as hereinbefore defined, R^(1′) is hydrogen orC₁₋₆-alkyl, R^(2′) is hydrogen or C₁₋₆—alkyl and R^(3′) is SiMe₂ orCH₂CH₂.
 5. A complex as claimed in claim 1 wherein R⁴ is methyl, tertbutyl, two R⁴ groups taken together form an indenyl ring or 4 R⁴ groupstaken together form a fluorenyl ring.
 6. A complex as claimed in claim 1wherein one R⁴ group represents a C₁₋₆ alkyl and two other R⁴ groups aretaken together to form an optionally substituted 6-membered fused carbonring.
 7. A complex claimed in claim 1 which has a substituent in5-position of the indenyl ligand.
 8. A complex claimed in claim 1 whichhas a substituent in 2-position of the indenyl ligand.
 9. A complexclaimed in claim 1 which has a tert-butyl substituent in 5-position ofthe indenyl ligand.
 10. A complex claimed in claim 1 which has a methylsubstituent in 2-position of indenyl ligand.
 11. A complex claimed inclaim 1 which has the following structure


12. An olefin polymerisation catalyst comprising: (i) a complexcomprising a metal ion coordinated by at least one ligand of claim 11;and (ii) a cocatalyst.
 13. A supported catalyst which contains a complexas claimed in claim
 1. 14. A supported catalyst as claimed in claim 13in which the support is contacted in the first stage with cocatalyst andthen in the second stage the complex is added into cocatalyst treatedcarrier.
 15. A process for the polymerisation of at least one olefincomprising polymerizing said at least one olefin in the presence of thecatalyst of claim 14.